XIX Congresso Nazionale Divisione di Chimica Industriale della

Transcription

XIX Congresso Nazionale Divisione di Chimica
Industriale della Società Chimica Italiana
SPONSOR
1
Comitato Scientifico
Presidente Giorgio Strukul
Fabrizio Cavani
Paolo Ciambelli
Claudio De Rosa
Martino Di Serio
Gaetano Guerra
Mario Marchionna
Francesco Pignataro
Paolo Pollesel
Anna Maria Raspolli Galletti
Ilenia Rossetti
Alessandro Scarso
Comitato Organizzatore
Coordinatore Riccardo Tesser
Maria Rosaria Acocella
Claudia Cioce
Anna Malafronte
Paola Rizzo
Vincenzo Russo
Maria Sarno
Oreste Tarallo
Rosa Turco
Vincenzo Vaiano
Rosa Vitello
2
PROGRAMMA SCIENTIFICO
14 Settembre
15:00-15:10 Apertura Congresso
Chairperson: Gaetano Guerra (UniSa)
15:10-15:50 Keynote Lecture dedicata ad Adolfo Zambelli: Claudio Pellecchia
“ Stereoselective Polymerization Catalysis: from “Tailor-made” Polyolefins to “Green
Plastics” in the Tradition of the Natta‟s School”
Sezione I (a): POLIMERI
Chairperson: Gaetano Guerra (UniSa)
15:50-16:05 Claudio De Rosa (UniNA)
“ Structure, Mechanical Properties and Stress-induced Phase Transformations of Cristalline
Elastomers”
16:05-16:20 Giuseppe Di Silvestro (UniMI)
“ Functional polycondensates of potential industrial interest ”
16:20-16:35 Alfonso Grassi (UniSA)
“ Synthesis and Applications of Styrene Copolymers; a 25 years long history at UniSA”
16:35-16:50 Elena Groppo (UniTo)
“ Looking at Ziegler-Natta catalysts from another perspective”
16:50-17:05 Luigi Cavallo (KAUST, UniSA)
“ A Unified Model Explaining Heterogeneous Ziegler-Natta Catalysis”
17:05-17:20 Coffee Break
Sezione II (b): POLIMERI
Chairperson: Finizia Auriemma (UniNa)
17:20-17:35 Placido Mineo (UniCT)
“ Synthesis, characterization and thermal properties of polymers based composite materials for
high power electronic packaging applications”
17:35-17:50 Rocco Di Girolamo (UniNA)
“ Cristalline-crystalline and cristalline-amorphous syndiotactic polypropylene based di-block
copolymers prepared by living olefin polymerization”
17:50-18:05 Fabio Curto (MAPEI)
“ Paper and packaging PVAc adhesives: performance and application process enhancement by
means of a rheological approach”
18:05-18:20 Andrea Pucci (UniPI)
“Self-healing and electronic conducting properties of a CNT/polymer composite”
18:20-18:35 Ivan Fuso Nerini (VINAVIL)
“ New generation of secondary suspending agents for the polymerization of VCM.
18:35-19:35 Assemblea Gruppo Interdivisionale di Catalisi
3
15 Settembre
Chairperson: Martino Di Serio (UniNa)
8:30-9:10 Keynote Lecture: Sesto Viticoli (AIRI)
“ La Ricerca Responsabile per la Chimica”
Sezione II : Il REACH e la Sicurezza dei prodotti chimici
Chairperson: Martino Di Serio (UniNa)
9:10-9:25 Biagio Naviglio (Staz. Sper. Industria delle Pelli, NA)
“ Tanning, leather and SVHC Substances”
9:25-9:40 Carla Zannoni (ENI Dow Lab, S. Donato)
“ A new GCxCX-MSD method tailored for REACH registration”
9:40-9:55 Matteo Guidotti (CNR INSTM, MI)
“ Bentonite clays as active sorbents: the genesis of a prototypal on-filed decontamination
device against chemical”
Sezione III (a) : CATALISI
Chairperson: Ilenia Rossetti (UniMi)
9:55-10:10 Roberto Esposito (UniNA)
“ A sustainable approach for the production of azelaic acid through oxidative cleavage of oleic
acid”
10:10-10:25 Caterina Barzan (UniTO)
“ The Comonomer Effect on the CrII/SiO2 Phillips Catalyst: First Spectroscopic Evidences”
10:25-10:40 Matteo Compagnoni (UniMI)
“ High-pressure photoreactor for CO2 conversion to fuels
10:40-11:00 Coffee Break
Sezione III (b) : CATALISI
Chairperson: Mario Marchionna (Saipem)
11:00:00-11:15 Almerinda Di Benedetto (UniNA)
“CFD modeling of novel reactor configurations for catalytic combustion”
11:15-11:30 Francesco Della Monica (UniSA)
“Dinuclear Iron(Iii) Complexes containing Thioether-triphenolate Ligand: Exceptionally
Active Catalysts for the Coupling of Carbon Dioxide with Epoxides for COCs Production”
11:30-11:45 Giorgio La Sorella (UniVE)
“Mimicking Enzymes: Fully Organocatalytic Alkyne Hydration Reaction with a
Supramolecular Self-Assembled Capsule”
11:45-12:00 Francesco Puzzo (UniBO)
“A new process for maleic anhydride synthesis from a renewable building block: the gas phase
oxydehydration of bio 1-butanol”
4
12:00-12:15 Massimiliano Mari (UniBO)
“The synthesis of nicotinic acid by gas-phase oxidation of -picoline: an analysis of key
catalyst features”
12:15-12:30 Angelo Vaccari (UniBO)
“On-board H2 production by partial dehydrogenation of fuels”
12:30-12:45 Ilenia Rossetti (UniMI)
“Process simulation and optimisation of H2 production from bioethanol and its use in fule
cells”
13:00-14:00 Lunch
Chairperson: Paolo Pollesel (ENI)
14:00-14:40 Keynote Lecture Medaglia Chiusoli: Alessandro Scarso (UniVE)
“Hugging Catalysts…If they Do Not Mind”
Sezione III (c): CATALISI
Chairperson: Giorgio Strukul (UniVe)
14:40-14:55 Nicola Schiaroli (UniBO)
“Amines formation in the Medium Temperature Water Gas Shift Reaction”
14:55-15:10 Tommaso Selleri (PoliMI)
“Low-T mechanistic analysis of NO oxidation and standard SCR over Fe- and Cu- zeolite
catalysts by chemical trapping techniques”
15:10-15:25: Federico Galli (UniMI)
“Nano and micro-TiO2 for the photodegradation of ethanol: experimental data and kinetic
modeling”
15:25-15:40: Amir Reza Fahami (PoliMI)
“Mechanistic Kinetic Modeling of NO Oxidation over Cu-chabazite”
15:40-15:55: Chiara Costabile (UniSA):
“Self-healing materials based on Ru and Ru-functionalized-graphene catalysts”
15:55-18:30: Poster Session and Coffee
18:30-19:30: Assemblea della Divisione di Chimica Industriale
20:00 Cena Sociale
5
16 Settembre
Chairperson: Angelo Vaccari (UniBo)
8.30-9.10: Keynote Lecture: Valentina Medri (CNR Faenza):
“How to tailor the porosity in geopolymer based materials”
Sezione IV : MATERIALI E PRODOTTI INORGANICI: sintesi e applicazioni
Chairperson: Angelo Vaccari (UniBo)
9:10 – 9:25: Anna Malafronte (UniNA)
“Fabrication of ordered arrays of Pd nanoclusters and PdO nanoparticles by using selfassembled block copolymers as templates”
9:25 – 9:40: Federico Bella (PoliTO)
“Industrially-scalable encapsulation of flexible, microfluidic and polymeric dye-sensitized solar
cells”
9:40 – 9:55: Alfonso Troisi (UniSa)
“Fe3O4/MoS2 and MoS2: comparisons based on morphological and electrochemical evaluations
for two innovative materials for supercapacitors. Features and prospects”
9:55-10:10: Francesco Malara (CNR ISTM, MI)
“Photodeposition vs. elettrodeposition of Ni(OH)2 co-catalyst on hematite electrodes for water
splitting application”
10:10-10:25: Elettra Papa (CNR ISTEC, Faenza)
“Insights into freeze casting of geopolymers”
Chairperson: Amilcare Collina (Mapei)
10:25-10:55: Invited Lecture: Giorgio Ferrari (Mapei)
“Innovative sustainable technologies for the construction industry”
10:55-11:15: Coffee Break
Sezione V : MATERIALI E PRODOTTI ORGANICI: sintesi e applicazioni
Chairperson: Federico Bella (PoliTo)
11:15-11:30: Giovanni Iannacone (PoliMI)
“Water-based reactive silver ink for flexible polymer solar cells and its interaction with the
polymeric hole-transporting layer”
11:30-11:45: Simone Galliano (UniTO)
“From organic solvents to water: a more sustainable approach toward industrially-upscalable
hybrid solar cells”
11:45-12:00: Valentina Sabatini (UniMI)
“Innovative printable self-cleaning material for covering photovoltaic cells”
12:00-12:15: Damiano Bandelli (UniFI)
“Palladium macrocomplexes based on Polymers and Copolymers from renewable resources”
Chairperson: Diana Sannino (UniSa)
12:15-12:55: Keynote Lecture: Paolo Ciambelli (UniSA)
“Carbon nanomaterials: from reserach to market. “
6
13:00-14:00: Lunch
14:00-15:00: Tavola Rotonda con AICIng sulle prospettive delle rispettive discipline
Sezione V : MATERIALI A BASE DI NANO CARBONI
Chairperson: Diana Sannino (UniSa)
15:00-15:15: Maria Rosaria Acocella (UniSA)
“Dual Role of Graphite Oxide Nanofiller in Thermosets Resins”
15.15-15.30: Michele Melchionna (UniTS)
“Exceptional activity of MWCNT@Pd/TiO2 nano hybrid catalyst in the photo reforming of
biomass derived alcohols”
15.30-15.45: Sara Andreoli (UniBO)
“Synthesis of ordered mesoporous carbon materials through soft-template method and their
characterization for catalytic application”
15:45-16:00: Candida Milone (UniME)
“Functional Carbon-Based Materials for Advanced Applications”
16:00-16:15: Marcello Casa (UniSA)
“Development and characterization of silver nano-particles supported on reduced graphene
oxide layers”
16:15: Chiusura Congresso
7
POSTER
POLIMERI
POLI-01: Oreste Tarallo (UniNA)
Isotactic Copolymers of Poly(1-Butene) with 1-Octene from Metallocene Catalysts:
Crystallization Behaviour and Mechanical Properties
POLI-02: Odda Ruiz de Ballesteros (UniNA)
Thermoplastic Elastomers from Binary Blends of Syndiotactic Polypropylenes with Different
Stereoregularity
POLI-03: Chiara Santillo (UniNA)
Crystal Structure of Isotactic Poly((R,S)3-Methyl-1-Pentene)
POLI-04: Claudia Cioce (UniNA)
Structural characterization of isotactic copolymers of propene with 1-octadecene from
metallocene catalysts
POLI-05: Giovanna Capuano (UniMI)
The use of novel PLGA-g-PVP amphiphilic copolymers for fabrication of nanostructured
materials
POLI-06: Christophe Daniel (UniSA)
Syndiotactic polystyrene fibers with nanoporous crystalline phases
purification applications
for water and air
POLI-07: Antonio De Nicola (UniSA)
Computational Study of Polypropylene melt: effect of stereoregularity on chain dimension
POLI-08: Laura Falivene (KAUST)
Mechanistic understanding of polar monomers polymerization
POLI-09:Rosita Lapenta (UniSA)
Polymerization and Copolymerization of L-Lactide and
Monoamidinate Titanium complexes
ε-Caprolactone promoted by
POLI-10: Paola Rizzo (UniSA)
Co-crystallization with low-molecular-mass guest molecules: a common route for getting
uniplanar orientations of polymer crystalline phases even in the absence of stretching
POLI-11: Miriam Scoti (UniNa)
Elastomeric properties and
poly(propylene-co-eicosene)
stress-induced
phase
transformations
of
syndiotactic
CATALISI
CAT-01: Rosa Turco (UniNa)
Supported Zinc complex for the esterification and transesterification of vegetable oils
CAT-02: Vincenzo Russo (UniNA)
Ru-based catalysts for γ-valerolactone synthesis
CAT-03: Rosa Vitiello (UniNA)
Synthesis of biolubricants by esterification using new heterogeneous catalysts
CAT-04: Claudia Bandinelli (UniBO)
One-pot Glycerol Oxidehydration to Acrylic Acid on Hexagonal-Tungsten-Bronze-Derived
Structures as Multifunctional Catalysts
8
CAT-05: Rodolfo Mafessanti (UniBO)
Development of innovative catalysts for methanation of syngas deriving from biomass
gasification
CAT-06: AngeloVaccari (UniBO)
New tio-resistant catalysts for on-board H2 production
CAT-07: Lorenzo Grazia (UniBO)
Selective reduction of furfural with MgO and Mg/Fe/O using methanol as H-transfer reactant
CAT-08: Mattia Melloni (UniBO)
Direct acid hydrolysis of lignocellulosic and cellulosic biomasses: Zr/P/O system vs. Nb/P/O
system
CAT-09: Andrea Malmusi (UniBO)
Synthesis of isoprene trough C4 – C1 coupling: substituting formaldehyde
with methanol, an investigation over the reaction mechanism
CAT-10: Chiara Dalla Valle (UniPD)
A new strategy for the obtainment of fluorinated resins as catalytic support
CAT-11: Antonella Salvini
(UniFI )
Transesterification of castor oil with trimethylchlorosilane for BioDiesel and αmonochlorohydrin production
CAT-12: Elisa Bertolucci (UniPI)
Green synthesis of ruthenium nanoparticles on magnetic carbon nanostructures and their use
for the selective hydrogenation of nitroaromatics
CAT-13: Caterina Barzan (UniTO)
Thermal- and Photo-Activation of CrVI/SiO2 Phillips Catalyst with Ethylene: Operando
Spectroscopic Evidences
CAT-14: Caterina Barzan (UniTO)
Cyclohexene and Methane as Reducing agents for CrVI/SiO2 Phillips Catalyst
CAT-15 : Caterina Barzan (UniTO)
Surface Reduction of TiO2 with Hydrosilanes: Conversion of Ethylene to HDPE Without
Alkylating Agent
CAT-16: Andrea Chiminazzo (UniVE)
1,2,3-Triazole Fluorescent Bisphosphonates as Osteoporosis Probes Drugs
CAT-17: Alberto Comazzi (UniMI)
Experimental results and dynamic simulation of enriched air production by water degassing for
process intensification
CAT-18: Alberto Comazzi (UniMI)
Co and Co/Ru based catalystssynthesized by FSP for the industrial Gas-to-Liquid FischerTropsch process
CAT-19: Nunzia Galdi (UniSA)
One Pot Synthesis Of Linear Alkylbenzenes From Styrene, Ethylene And Hydrogen
CAT-20: Giuseppina
Iervolino (UniSA)
Photocatalytic removal of Patent Blue V dye on Au/TiO2 catalysts
CAT-21: Paola Lanzafame (UniME)
Role of acid sites in porous silica catalysts for selective production of biodiesel additive
CAT-22: Federica
Menegazzo (UniVE)
Selective oxidations of biomass resources on Au/ZrO2 catalysts doped by sulphates
CAT-23: Annarita Noschese (UniSA)
Selective and Efficient Reduction of Nitrobenzene to Aniline catalyzed by AuNPs Embedded in
a Nanoporous Crystalline Polymeric Support
9
CAT-24: Alberto Olivo (UniVE)
Study of photoreactor design for sustainable carbon dioxide photoreduction
CAT-25: Fabrizio Puleo (CNR PA)
B-site Pd and Ni promoted La0.6Sr0.4Co0.2Fe0.8O3-δ perovskites as IT-SOFCs cathodes
CAT-26: Elisabetta Rombi (UniCA)
Hard-Templated NiO-CeO2 mixed oxides as catalysts for CO2 methanation
CAT-27: Maria Pia Ruggeri (PoliMI)
An innovative method for the estimation of AN storage over commercial Cu-zeolite catalysts for
automotive applications
CAT-28: Tommaso Selleri (PoliMI)
Experimental and modeling study of hydrocarbon inhibition effects on NH 3-SCRover metal
promoted zeolite catalysts
CAT-29: Claudia Antonetti (UniPI)
Heterogeneous catalysis for the production of 5-hydroxymethyl-2-furfural and of 2,5bis(hydroxymethyl)furan from fructose and inulin
MATERIALI E PRODOTTI INORGANICI
INORG-01: Federico Bella (PoliTO)
Industrially-scalable encapsulation of flexible, microfluidic and polymeric dye-sensitized solar
cells
INORG-02: Claudia Cirillo (UniSA)
Graphene Coated FeCo Nanoparticles for Supercapacitors
INORG-03: Claudio Evangelisti (CNR MI)
Gold nanoparticles obtained by aqueous digestive ripening: their application as X-ray contrast
agents
INORG-04: Giorgio Ferrari (MAPEI)
New sustainable technology to recover returned concrete
INORG-05: Olga Sacco (UniSA)
Improving visible light active photocatalyst performances through photoactive supports in the
photocatalytic removal of emerging contaminants
INORG-06: Giuseppe Sarno (UniSA)
Photocatalytic Properties of N-Doped TiO2 Functionalized Ceramic Tiles under UV and
Visible Light Irradiation
INORG-07: Vincenzo Venditto (UniSA)
Monolithic nanoporous-crystalline aerogels with sulfonated amorphous phases: fast and
efficient polymer materials for removing VOCs from water
INORG-08: Mario Maggio (UniSA)
Graphite and graphene oxide paper
10
MATERIALI E PRODOTTI ORGANICI
ORG-01: Marialuisa Siepi (UniNA)
Denatured Lysozyme: a new tool to solubilize carbon nanomaterials
ORG-02: Damiano
Bandelli (UniFI)
Pyrolysis of α-cellulose with multimode microwave oven
ORG-03: Stefano Antenucci
(UniMI)
Intrinsic antioxidant bio-based polymer for food active packaging
ORG-04: Federico Galli (UniMI)
Polyhydroxyalkanoate extraction from biomass using environmentally friend techniques
ORG-05: Eleonora Macedi (UniSA)
Guest activated organic functional materials
ORG-06: Gabriele Milani (PoliMI)
Experimental and Finite Element optimization of the production process of rubber insulated
electric cables vulcanized with steam water
ORG-07: Stefania Pragliola
(UniSA)
Characterization and Optoelectronic Applications of Highly Stereoregular Polymers
Containing Carbazole
REACH e Sicurezza
REACH-01:
Anna
Basco (CNR NA)
The impact of hazardous substances in the case of structural failure of oil and gas offshore
platform
11
ORAL COMMUNICATIONS ABSTRACTS
12
Congresso Divisione Chimica Industriale
Salerno, Settembre 2015
Structure, Mechanical Properties and Stress-induced Phase Transformations of
Crystalline Elastomers.
Miriam Scoti, Finizia Auriemma, Rocco Di Girolamo, Odda Ruiz de Ballesteros, Claudio
De Rosa*
Dipartimento di Scienze Chimiche, Università di Napoli “Federico II, Complesso di Monte
Sant'Angelo via Cintia, 80126 Napoli, Italy
Syndiotactic polypropylene (sPP) and copolymers of sPP with other 1-olefins are a new class of
thermoplastic elastomers, where crystallinity, Young modulus, mechanical strength and
elasticity can be tailored through choice of type and concentration of the comonomer and
concentration of stereodefects in sPP homopolymer. In this communication we report a study of
the structure and mechanical properties of copolymers of sPP with other 1-olefins, from
ethylene to long branched olefins, such as 1-eicosene. The relationships between structure and
stress-induced phase transformations and mechanical properties have been clarified. The
copolymer samples have been synthesized with a syndiospecific Cs metallocene catalyst in a
wide range of comonomer concentrations. All copolymer samples show good ductility, high
modulus and good elastic properties. Incorporation of long branched comonomers allows
decrease of the glass transition temperature already for low comonomer concentrations. The
polymorphic transformations occurring during deformation have been studied by recording Xray diffraction during stretching and relaxation. In samples with low comonomer content
defective crystals of form I partially transform by stretching into the trans-planar form III of
sPP, and the elastic recovery is associated with the polymorphic transition of the metastable
trans-planar form III into the more stable helical form II that occurs upon releasing the tension.
This transition provides an enthalpic contribution to the elasticity. 1 High concentrations of
ethylene comonomeric units stabilize the trans-planar modifications, whereas high contents of
long branched comonomers stabilize the helical forms (form I or form II), preventing in both
cases the occurrence of the reversible phase transformation during stretching and relaxation.
Therefore, samples with high comonomer concentrations, showing very low crystallinity,
present the classic entropic elasticity, due to the reversible transition between extended and
random coil conformations of the amorphous chains. In conclusion, these copolymers are a new
class of crystalline elastomers characterized by different types of elasticity, enthalpic or
entropic, depending on the type and concentration of the comonomeric units and crystallinity.
Keywords: Thermoplastic elastomers, enthalpic elasticity, syndiotactic propene copolymers
* Corresponding author: [email protected]
References
[1] F. Auriemma, C. De Rosa, S. Esposito, G. R. Mitchell, Angew. Chem. Int. Ed., 46 (2007)
4325.
13
Functional polycondensates of potential industrial interest
G. Di Silvestro*, M.A. Ortenzi, H. Farina, V. Sabatini, S. Antenucci
Università degli Studi di Milano, Dipartimento di Chimica, Centro di Ricerca Coordinata
(CRC) sui polimeri”LaMPo”, Via Golgi 19, Milano
Polycondensation is the oldest polymerization process useful for technopolymers ( Polyamides,
aromatic polyesters, polycarbonates, PES, PEEK and, with some limits, PLA).
Most of these materials are obtained via an high energy consuming process and from oil
derived monomers. More sustainable processes can consider or new applications for a polymer
without new investments or by using monomers from renewable source or, the best case, by
optimizing a materials, already synthetized, from renewable source.
In all cases a perfect control of the chain growth process is mandatory.
In the presentation will be discussed some results of potential interest for industry.
Keywords: Polycondensation, Polyamides, Polyesters, PES, PEEK, PLA
Corresponding authot: *[email protected]
References:
G. Di Silvestro, M.A. Ortenzi, H. Farina, L. Basilissi. Polymers with complex macromolecular
architecture having flame-retardant properties PCT Int. Appl. (2015), WO 2015000995 A1
20150108
G. Di Silvestro, C.M. Yuan, M. Ortenzi, H. Farina, T. Lugato, L. Basilissi. Branched lactic acid
polymers with high viscosity in the molten state and high shear sensitivity, and nanocomposites.
PCT Int. Appl. (2013), WO 2013008156 A1 20130117.
G. Di Silvestro, F. Speroni, C.M. Yuan, H. Zhang. Polyamides with high fluidity, their
preparation and compositions.PCT Int. Appl. (1999), WO 9964496 A1 19991216.
S. Giordano, M. Longhi, L. Formaro, H. Farina, G. Di Silvestro. Electrochemical behavior of
PES ionomer and Pt-free catalyst for PEMFCs. Journal of Electrochemical Science and
Engineering 3(3), (2013), 115-123.
L. Basilissi, G. Di Silvestro, H. Farina, M.A. Ortenzi. Synthesis and characterization of PLA
nanocomposites containing nanosilica modified with different organosilanes II: Effect of the
organosilanes on the properties of nanocomposites: Thermal characterization. Journal of
Applied Polymer Science 128(5), (2013), 3057-3063.
C.M. Yuan, G. Di Silvestro, F. Speroni, C. Guaita, H. Zhang. Control of macromolecular
architecture of polyamides by poly-functional agents, 1: theoretic and experimental approaches
to star-branched polyamides. Macromolecular Chemistry and Physics 202(10), (2001), 20862092.
G. Soliveri, V. Sabatini, H. Farina, M.A. Ortenzi, D. Meroni, A. Colombo.
Double side self-cleaning polymeric materials: the hydrophobic and photoactive approach.
Colloids and Surfaces A: Physicochemical and Engineering Aspects, in press
V. Pifferi, S. Checchia, L. Falciola, G. Di Silvestro, H. Farina, A. Strazzeri, M. A. Ortenzi.
Casting solvent effect in the electroanalytical performances of sulphonated poly(aryl ether
sulphone) modified electrodes. Submitted
14
Synthesis and Applications of Styrenic Copolymers; a 25 years long history at UniSA
Alfonso Grassi,1* Antonio Buonerba,1 Carmine Capacchione,1 Stefano Milione1
1 – Dip. Chimica e Biologia, Università degli Studi di Salerno, via Giovanni Paolo II, Fisciano
(SA), Italy.
The successful achievement of stereospecific metal catalyzed styrene polymerization using
Ziegler Natta catalysts opened in the early 90s a new frontier in the synthesis of stereoregular
copolymers of styrene (S) with 1,3-conjugated dienes.[1] Block and random copolymers,
comprising styrenic polymer segments with syndiotactic or isotactic arrangements depending
on the metal catalyst precursor, were synthesized and fully characterized: they found
application as nanofiller, acidic catalyst after sulfonation, nanoporous support of gold
nanoparticles applied in sustainable redox catalysis.[2]
Stereoregular syndiotactic polystyrene-co-cis-1,4-polybutadiene copolymers resulted
particularly effective as support for gold nanoparticles as green catalyst for the selective
aerobic oxidation and direct esterification of alcohols, as well as for the reduction of
nitroarenes, where the permeable polymer matrix act as concentrator for the reactants towards
the catalytic sites.[3]
Recently, the growing interest for biosourced polymers prompted us to search for new
bioderived monomers suitable for the synthesis of functional styrenic copolymers. 2-vinylfuran
(VF) was synthesized by Peterson methylenation of furfural, a cheap chemical resulting from
chemical degradation of lignocellulosics.[4] Ideal ATR copolymerization of styrene with 2vinylfuran yielded random copolymers (S-co-VFs) in a wide range of composition. The S-coVFs are stable in solution and solid state at room temperature for years; thermal decomposition
starts only at temperature higher than 380°C. The glass transition temperature decreases as the
VF concentration is increased, reaching the lowest value of 54°C for a VF mole fraction of
0.60. A number of application have been designed using Diels−Alder reaction of S-co-VF with
maleimide derivatives based on the reversible crosslink, the self-healing, the shape memory
effect and the recyclability properties of this novel functional copolymers.
Keywords: styrene copolymers, ,dienes, biosourced polymers.
*Corresponding author: [email protected]
References
[1] Grassi, A.; Caprio, M.; Zambelli, A.; Bowen, D. E., Macromolecules 2000, 33 (22), 8130.
[2] (a) Buonerba, A.; Speranza, V.; Grassi, A., Macromolecules 2013, 46 (3), 778; (b)
Buonerba, A.; Cuomo, C.; Sánchez, S.; Canton, P.; Grassi, A., Chem. Eur. J. 2012, 18 (2), 709.
[3] Buonerba, A.; Noschese, A.; Grassi, A., Chem. Eur. J. 2014, 20 (18), 5478.
[4] Ortega Sánchez, S.; Marra, F.; Dibenedetto, A.; Aresta, M.; Grassi, A., Macromolecules
2014, 47 (20), 7129.
15
Looking at Ziegler-Natta catalysts from another perspective
Elena Groppo1*, Thushara KS1, Alessandro Piovano1, Silvia Bordiga1
1 – Department of Chemistry and INSTM, University of Torino, via Quarello 15, 10135 Torino,
Italy
Heterogeneous Ziegler-Natta (ZN) catalysts for polyolefins production are among the most
employed and versatile catalysts in chemical industry, and probably those having the largest
impact in every days life. The extraordinarily large number of polymer architectures today
available and the remarkable rapid progress in polyolefin technology, are closely associated
with catalyst‟s development. Since their discovery in 1960s, heterogeneous ZN catalysts have
progressed enormously. Most of the breakthrough in this field were the result of a trial-anderror approach, whereas a full elucidation of the catalyst‟s structure by means of experimental
methods is much less widespread. The majority of experimental information available in the
literature come from detailed analysis of the microstructure of produced polypropylene [1],
rather than the catalyst itself. Direct investigations of the active species in ZN catalysts is less
common and so far most of them were focused on the pre-catalysts only, i.e. the system before
interaction with the activator, usually an alkyl-aluminum compound. Although the properties of
the pre-catalyst might have an influence on those of the catalyst derived from it, it was recently
demonstrated that the activator causes substantial transformation in the pre-catalyst, involving
the whole catalyst components and not only the active phase [2]. Therefore, elucidation of the
catalyst structure requires the ability to investigate the system in presence of the activator, if not
in presence of both the activator and the olefin monomer.
In this contribution we propose new experimental approaches, based on the synergic
application of several characterization techniques [3], to look at ZN catalysts from another
perspective. We demonstrate that in situ de-alcoholation of MgCl2-nROH adducts is an efficient
and versatile method to obtain nano-crystalline MgCl2 having a large surface area and exposing
catalytically relevant (104) and (110) faces, whose relative proportion can be tuned by changing
the starting alcohol. FT-IR spectroscopy of CO adsorbed at 100 K revealed to be a powerful
tool to characterize the exposed MgCl2 surfaces, before and after adsorption/reaction with TiCl 4
and/or electron donors (ED). It is demonstrated that TiCl 4 can only adsorb on the MgCl 2(110)
surface and also EDs preferentially adsorb on the same surface. More important, both EDs and
AlR3 easily react with TiCl4 weakly bonded to the (110) face, forming homogeneous-like
complexes which are in large extent detached from the MgCl 2 surface. These results re-open the
old question on the role of MgCl2 in ZN catalysis. Once more (as in other fields of catalysis) the
border between homogeneous and heterogeneous catalysis is gradually disappearing.
Keywords: Ziegler-Natta catalysts, spectroscopy, polymerization
References
[1] V. Busico, R. Cipullo, Prog. Polym. Sci. 26 (2001) 443
[2] K. Seenivasan, A. Sommazzi, F. Bonino, S. Bordiga, E. Groppo, Chem. Eur. J, 17 (2011)
8648
[3] E. Groppo, K. Seenivasan, C. Barzan, Catal. Sci. Technol., 3 (2013) 858
16
A Unified Model Explaining Heterogeneous Ziegler-Natta Catalysis
Raffaele Credendino,1 Dario Liguori,2 Giampiero Morini,2 and Luigi Cavallo1,3,*
1
Kaust Catalysis Center, King Abdullah University of Science and Technology (KAUST),
Thuwal 23955-6900, Saudi Arabia. 2G. Natta Research Center, LyondellBasell Polyolefins,
Piazzale G. Donegani 12, 44100 Ferrara, Italy. 3Dipartimento di Chimica e Biologia,
Università di Salerno, Via Papa Paolo Giovanni II, Fisciano, Italy
We propose a model for MgCl2 supported Ziegler-Natta catalysts capable to reconcile the
discrepancies emerged in the last 20 years, when molecular models corresponding to possible
catalytic species adsorbed on the (110) and (104) MgCl2 facets, were used to rationalize the
experimental data. Specifically, we show that low-energy step defects on the neglected but
thermodynamically more stable (104) facet of MgCl2 can lead to sites for strong TiCl4
adsorption, comparable to TiCl4 adsorption on the (110) facet. The corresponding Ti-active site
is scarcely stereoeselective, and its stereoselectivity can be enhanced by coordination of Alalkyls or Lewis bases in the close proximity, similarly to what proposed for Ti active species
adsorbed on the (110) facet. The surface energy of the step defected (104) MgCl 2 facet is
clearly lower than that of the well accepted (110) facet. Indeed, combined with previous
knowledge on the (110) facet, the newly proposed site provides a conceptual scheme explaining
a large fraction of the experimental results.
Keywords: Ziegler-Natta catalyst, DFT, heterogeneous catalysis
Correspondig author: [email protected]
17
Synthesis, characterization and thermal properties of polymers based composite materials
for high power electronic packaging applications
Placido Mineo,1 Fabiola Spitaleri,1 Emilio Scamporrino1
1- Dipartimento di Scienze Chimiche and I.N.S.T.M. UdR of Catania, Università di Catania,
Viale A. Doria, 6, 95125 Catania, Italy
The aim of the power electronics devices is the electrical energy conversion by means of
several devices (inverter, transformer, chopper, etc.) trying to minimize the dissipated power.
However, each device has a maximum operability temperature and,in absence of a good heat
transfer from device to outside, an excessive power and/or temperature increasing could
determine the device‟s breaks.In this contest, the device‟s packaging can play an important role
in the thermal dissipation and/or in determining its good electronic performance.
In general, in a power module, all objects surrounding the die constitute the Package 1. Its
functions are: i) heat dissipation; ii) protection of the chip
from environmental agents; iii) make it more handy. For the
device performance very important is the point i) and, often,
anindustrial microelectronic's goal isthe improvement of the
thermal efficiency of the electronic packaging which can
contribute to a higher performance and a longer life.
In this work the synthesis and characterization of new
composites materials2, able to improve the thermalefficiency
of an electronic device packaging, are described. In particular, because the thermal efficiency
depend on the degradation temperature and/or the thermal conductivity, several composites
based on epoxy resins and suitable fillers having an high thermal performance, have been
considered. All compositesand their precursors have been thermally and structurally
characterized. The obtained composites have a start degradation temperature, in air, higher than
the maximum reached by the latest generation devices (about 250 °C), this makes possible their
use in the microelectronic packaging.
Finally, two methods for the conductivity measurement have been developed, a direct and an
indirect procedure, and both tested examining several synthesized packaging.
Keywords: Organic composites, Electronic devices, Synthesis, Characterization
* Corresponding author: Placido Mineo, [email protected]
References
[1] Y. Liu in “Power Electronic Packaging: Design, Assembly Process, Reliability and
Modelling”, New York, Springer, (2012)
[2] P. Mineo, F. Spitaleri, S. Patanè, E. Scamporrino, Macromolecules, submitted.
18
Crystalline-crystalline and crystalline-amorphous syndiotactic polypropylene based diblock copolymers prepared by living olefin polymerization
Rocco Di Girolamo*1, Finizia Auriemma1, Ivana Pierro1, Annette Thierry2, Geoffrey W.
Coates3, Bernard Lotz2 and Claudio De Rosa1
1
Dipartimento di Scienze Chimiche, Università di Napoli "Federico II", Napoli, Italy
Institut Charles Sadron, Strasbourg, France
3
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY (USA)
2
We report the morphology, structure and mechanical properties of semicrystalline, polyolefinbased block copolymers (BCPs) with the aim of obtaining ordered nanostructures and
innovative thermoplastic elastomers.
By using living, stereoselective insertion polymerization catalysts, syndiotactic polypropyleneblock-poly(ethylene-co-propylene) (sPP-b-EP) and syndiotactic polypropylene-blockpolyethylene (sPP-b-PE) were synthetized.1
Thin films of BCPs were prepared from solution by dip-casting. The formation of large-sized,
well-oriented lamellar nanostructures of BCPs composed of a crystallizable sPP block linked to
an amorphous rubbery block EP (sPP-b-EP) was successfully achieved by using epitaxial
crystallization2 with p-terphenyl as substrates. TEM bright field images and electron diffraction
patterns of gold decorated nanostructures reveals the presence of well oriented crystalline
lamellae ordered over large area alternated to amorphous layers.
Crystalline-crystalline block copolymers (sPP-b-PE) epitaxially crystallized onto crystals of pterphenyl show a more complex lamellar morphology. For BCPs with high volume fraction of
sPP block only one lamellar orientation can be observed. In this case sPP crystallize first. For
sPP-PE BCPs with similar block lengths, TEM images show regions characterized by double
orientation of PE lamellae due to the epitaxial relationship of PE with p-terphenyl. In these
regions PE crystallize first. They alternate with regions presenting a single lamellar orientation
of sPP according to the epitaxial relationship with p-terphenyl. In these regions sPP crystallize
first. In other words the block that crystallize first determines the local morphology.
An analysis of the mechanical properties and a detailed structural study of BCPs have been
performed in order to clarify the effects of the presence of crystalline (PE) or amorphous (EP)
block on the crystallization behavior of sPP, and in particular on the stress-induced
transformations.3
Keywords: block copolymer, semicrystalline, nanostructures
References:
[1] J. Tian, D. Hustad, G.W. Coates. J. Am Chem. Soc. (2001), 123, 51343.
[2] C. De Rosa, C. Park, E. L. Thomas, B. Lotz. Nature (2000), 405, 433
[3]De Rosa, C.; Ruiz de Ballesteros, O.; Santoro, M.; Auriemma, F. Macromolecules (2004),
37, 1816.
19
Paper and packaging PVAc adhesives: performance and application process enhancement
by means of a rheological approach
S. Carrà1, F.Chiozza2, F. Curto3*, M. Ferraioli2
1 - Mapei S.p.A., (Tileadhesives Department, via Cafiero, 22 – Milano (MI) Italy)
2 - Vinavil S.p.A.,( R&D Department, via Toce, 7 – Villadossola (VB) Italy)
3 - Mapei S.p.A., ( Rheology Department, via Cafiero, 22 – Milano (MI) Italy)
Water based vinylacetate polymers dispersions [1] are widely used in packaging and paper
industry thanks to their good adhesion properties to the specific involved substrates (paper,
cardboard, plastic foils, varnished or coated surfaces and metals), to their solvent free
composition, high versatility in terms of viscosity range and equipment suitability, high
mechanical properties in critical condition, low migration properties. Recent market
investigations have confirmed that paper and packaging industry is one of the most exciting and
challenging operating unit. In fact, increasing and specific needs of the end users acting in the
very well-known business like food, luxury and graphic art packaging, obliged the sector
operators to develop a huge number of processes by increasing the quality and maximizing the
profits. In this context the glue plays a very important role because is driving the main output of
the paper chain that is the packaging design/assembly. This work is introducing a study on a
polymeric adhesive able to satisfy the process requests. The suitability of polyvinyl-acetate
based glues is well known in the paper industry. The tuning of the formula composition of the
glue has been investigated in order to optimize the process parameters [2]. Some tests,
commonly applied in order to investigate the glue properties ideal for paper industry
application, have been carried out and, among them, wet tack development, delamination and
mechanical properties. This presentation describes the options of the standard adhesive
formulation and presents the possibility to help the formulator through alternative and
simplified methods like rheological characterization [3]. The use of rheology allowed to predict
the best performances of the adhesive used for packaging by combining the results from a stress
controlled and capillary rheometers. The flow curves in a wide range of shear rates give a
prediction of the behaviors of the glue both at initial flowing state and at regime state (105 s-1of
shear rate). Chemical modification of the adhesive formulation in order to avoid instability has
been investigated by means of shear thinning behavior. Furthermore dynamic measurements
have been carried out highlighting that under oscillatory shear, the elastic modulus of some glue
formulations showed a weak dependence on frequency over the range 1-100Hz. The apparent
viscosities, pseudoplasticity, yield stress of different adhesives are all dependent on their
formula composition. A proper comprehension of rheological approach applied to the specific
industry guarantees the maximum efficiency of the entire packaging process.
Keywords: adhesive, rheology, wet tack, mechanical methods
*Corresponding author: F. Curto, [email protected] tel.0237673915
References
[1] H. Warson, C. A. Finch: “Application of synthetic resin latices”. Ed. John Wiley & Sons Ltd, Baffins
Lane, Chichester, England, 2001, 8, 484-512.
[2] Fabio Chiozza (Vinavil S.p.A.): “Dispersioni vinil-etileniche per il settore adesivi per cartotecnica e
imballaggio”. AVISA congress, 2001.
[3] T.G. Mezger “The rheology Handbook”. Ed.Vincentz.
20
Self-healing and electronic conducting properties of a CNT/polymer composite
R. Araya-Hermosilla1, Patrizio Raffa1, Giovanni Fortunato2, A. A. Broekhuis1, F.
Picchioni1 and Andrea Pucci2*
1 - Department of Chemical Engineering/Product technology, University of Groningen,
Nijenborgh 4, 9747AG, Groningen, The Netherlands
2 - Department of Chemistry and Industrial Chemistry, University of Pisa, Via Moruzzi 3,
56104 Pisa, Italy
Abstract
Polymer composites based on carbon nanotubes (CNT) and with intrinsic self-healing
properties have been considered as a good option for the production of flexible and light longlasting materials for electronics. In this work, a CNT/polymer composite presenting selfmendable characteristics was designed and prepared by mixing polyketone (PK) grafted with
OH groups (PK-OH) and pristine MWCNTs (Figure 1). The polymer itself displays self-healing
properties at room temperature (RT) due to the reconnection of cracked edges via hydrogen
bonding. Notable is the fact that the homogeneous incorporation of CNTs increases the
material‟s modulus and allows electronic conduction. Experiments have shown that the healing
process is easily achieved by slightly compressing or heating up the composite. It was also
found that the electrical resistivity decreases by increasing the temperature, and the negative
temperature coefficient, typical of thermistors, can be measured in a broad range of
temperatures, between RT and the glass transition (Tg). Overall, the present resultssupport the
use ofpolyketonenanocompositeas a potential candidate for self-healing electronics aimed at
prolonging the lifetime of electronic devices for waste reduction.
Figure 1. Chemical design of PKnanocomposite
Keywords: polymer composites, self-healing properties, electronic conductivity
* Corresponding author: Andrea Pucci, [email protected]
References
[1] R. Araya-Hermosilla, A. A. Broekhuis, F. Picchioni, Eur.Polym. J.50(2014)127
[2] N. Calisi, A. Giuliani, M. Alderighi, J. M. Schnorr, T. M. Swager, F. Di Francesco, A.
Pucci, Eur.Polym. J.49(2013) 1471
21
New generation of secondary suspending agents for the polymerization of VCM
Ivan Fuso Nerini
VINAVIL
SpA,
Cell.3356366843
Special
Projects,
Via
Valtellina
63-20159
Milan
With an annual production of ca. 40 million tons PVC is one of the most widely used plastics in
the world and used in many applications like housing, automotive, healthcare, electrical,
packaging, fashion and sports. The annual growth rate of the polymer is estimated at around
4%. Although the PVC industry is a mature industry that was born in 1936, the production
technology is constantly evolving to improve performance and to adapt the process and product
to the increasingly stringent standards for the protection of workers, consumers and the
environment.90% of the PVC production is made by suspension polymerization [1,3]which takes
place in the presence of suspending agents generally consisting of polyvinyl alcohols with
different Hydrolysis Degrees (HD): the "primary" agent having high HD and possibly the
"secondary" (low HD) if it is necessary to obtain uniform polymer particles with high porosity.
The high porosity of the polymer allows to totally eliminate the unreacted VCM in a short time
and to promote the absorption of the other additives and plasticizers.Thesecondarysuspending
agentisusedfor almost a quarterof world productionofthisplastic material(about 10 million tons).
VINAVIL S.p.A. produces secondary suspending agents and has developed a new generation
product, based on an acrylic copolymer highly hydroxylated, which allows to obtain significant
advantages in respect of known technique. The product is manufactured by radical
polymerization in polar solvent from different acrylic monomers and subsequently it is brought
in aqueous emulsion as nanolattice.
The new suspending agent, which was developed in co-operation with a leading Company in
PVC technology, is used in quantities significantly lower than those of the standard product
(polyvinyl alcohol with low HD) and allows: to significantly reduce the stripping time for the
unreacted VCM removal; to improve the next stage of processing obtaining a significant
reduction of fish-eyes which are optical imperfections in the transparent films due to a defective
absorption of the additives used; to decrease the energy consumption in the stripping step of the
monomer also obtaining an improvement of the color in dependence of the milder conditions of
the process.
Furthermore the manufacturing of this type of suspending agent takes advantage of an higher
productivity in comparison with the previous technology.
Keywords: VCM polymerization, suspension polymerization, suspending agent.
References
[1]Smallwood, P.V. Vinyl Chloride Suspension polymerisation and the control fo polymer
properties, Makromol. Chem. Symp, 1989, 29, 1.
[2]Talamini, G.; Visentini, A; Kerr, J. Bulk and Suspension polymerisation of Vinyl Chloride:
the two-phase model, Polymer 1998, 39(10), 1879.
22
A new GCxGC-MSD method tailored for REACH registration
Carla Zannoni*, Cristina Flego, Luciano Montanari
eni – Research & Technological Innovation - DOW LAB (Via Maritano 26, S. Donato
Milanese – 20096 Italia)
Recently, ECHA (European CHemical Agency) expressed the need of additional data on
hazardous properties of petroleum substances to facilitate the evaluation task of their
applicability. This caused fundamental changes in the analytical approach and in classification
and labelling in Europe. In particular, ECHA requires the production of updated dossiers for
certain categories, in order to cover the data gap on toxicity by new testing proposals. However,
CONCAWE (CONservation of Clean Air and Water in Europe) developed in 2005 general
guidance for registration of petroleum and derivatives under REACH (Registration, Evaluation
and Autorisation of Chemicals) and updated regulations become stringent.
Among the analytical techniques specified by REACH, chromatographic methods provide some
discrimination between the components, although limited by both their resolving power and the
relative complexity of the substance under investigation. For these reasons, CONCAWE has
invited their participants to apply comprehensive two-dimensional gas-chromatography
(GCxGC) for obtaining a more detailed composition on petroleum.
Eni, member of CONCAWE, has decided to follow these indications, developing and
optimizing a proper analytical method based on GCxGC coupled with Mass Spectrometry
Detector (GCxGC-MSD). This method involves separation using two GC columns: the first one
separates according to boiling point of the compounds, the second one according to their
polarity. The fractions coming from the first column are isolated, heart-cutted, and transferred
by a modulator device to the second column for further separation. The accurate identification
of each species is obtained by MSD that allows a greater identification capability with respect
to other detectors (e.g. FID). The outcome is a series of high-speed chromatograms, displayed
as a contour plot, with the x and y-axis representing the retention time respectively from the
first and the second column. The chemical classes are separated according to their increasing
mass and polarity, from apolar species (e.g. paraffins) in the lower part of the plot to the most
polar ones (e.g. crysenes) in the upper part of the plot. A template has been also developed and
applied to define the eluting area of the different chemical classes and inside a certain chemical
class, the species with the same number of carbon atoms.
Different petroleum distillation cuts and improved fuel mixtures, with boiling point below
470°C (i.e. C35), are studied. This method provides one detailed quantitative map on the
components (e.g. n- and iso-paraffins, naphthenes, mono-, di-, tri, tetra-aromatics) for each
number of carbon atom and, in particular, it may evidence the presence in traces of SVHC
(Substances of Very High Concern), such as anthracene.
The GCxGC-MSD approach here described gives greatly enhanced separation of the numerous
constituents present in petroleum substances with respect to more conventional
chromatographic and spectroscopic methods and candidates itself as official analytical method
applied for registration of petroleum and petroleum derivatives under REACH.
Keywords: REACH, GCxGC-MSD, petroleum substances
* Corresponding author: Carla Zannoni: [email protected]
23
Bentonite clays as active sorbents: the genesis of a prototypal on-field decontamination
device against chemical warfare agents
Matteo Guidotti1*, Rinaldo Psaro1, Chiara Bisio1,2, Fabio Carniato2, Leonardo Marchese2,
Mykola F. Starodub3, Andrew M. Katsev4, G. Cinquantini5
1 - ISTM-CNR Istituto di Scienze e Tecnologie Molecolari, Milano, Italy
2 - DiSTI, Nano-SiSTeMI Centre, Univ. of Eastern Piedmont A. Avogadro, Alessandria, Italy
3 - National University of Life and Environmental Sciences of Ukraine, Kyiv, Ukraine
4 – “V.I. Vernadsky” Crimean Federal Univ. Medical Academy, Simferopol, Crimea, Russia
5 – NBCsystem srl, loc. Volaparo, Blera (VT), Italy
The abatement of highly toxic chemical warfare agents (CWA) is commonly based on the use
of strong oxidants with high environmental impact or via thermal degradation. A new class of
chlorine-free catalytically active sorbent solids, able to promote the oxidative degradation and
sorption of toxic organosulfur (blistering) and organophophorus (nerve) CWA into non-noxious
products, is therefore proposed.
Transition metal-containing bentonite clays were identified as potential catalysts for the CWA
oxidative abatement in the presence of hydrogen peroxide as an oxidant. The active transition
metal was added via a post-synthesis approach in order to obtain a final bifunctional catalyticsorbent material which is capable to promote at best the oxidising capabilities of H2O2 [1] and
to show a marked acid character [2].
The decontamination performance of the metal-bentonite materials were evaluated at room
temperature in the oxidative degradation, of (2-chloroethyl)ethyl sulfide (CEES) and
dimethyl(methylphosphonate) (DMMP), simulants of blistering (yperite) and nerve agents,
respectively, with solid oxidants able to release in situ H2O2, The innovative formulations have
been compared with a conventional decontamination powder in use by the Italian Armed Forces
(M75 powder), containing calcium hypochlorite, as an active oxidant.
The toxicological impact on the environment and on living organisms
was also assessed by biotoxicity tests on bioluminescent bacteria (P.
leiognathi Sh1) and vegetable plants (Phaseolus vulgaris).
The powder formulation has been loaded in a prototypal on-field
portable device, specifically conceived for professionals operating in
high-risk emergency contaminated scenarios (first responders, armed
forces, police units, etc.).
Financial support from NATO through SPS project “NanoContraChem”
(984481) is acknowledged.
Keywords: decontamination formulation, catalytic abatement, chemical warfare agents, clays
* Corresponding author: Matteo Guidotti, [email protected]
References
[1] F. Carniato, C. Bisio, R. Psaro, L. Marchese, M. Guidotti, Angew. Chem. 53 (2014) 10095
[2] L. Ostinelli, S. Recchia, C. Bisio, F. Carniato, M. Guidotti, L. Marchese, R. Psaro, Chem.
Asian J. 7 (2012) 2394
24
A sustainable approach for the production of azelaic acid through oxidative cleavage of
oleic acid
Vincenzo Benessere, Maria E. Cucciolito, Martino Di Serio, Roberto Esposito*, Fiorella
Nugnes, Francesco Ruffo, Rosa Turco
Dipartimento di Scienze Chimiche, Università di Napoli “Federico II” and Consorzio
Interuniversitario di Reattività Chimica e Catalisi (CIRCC)
Biomass is attracting increasing attention for the production of energy and chemicals.
In this frame, unsaturated acids derived from vegetable oils are of particular interest, especially
because their oxidation leads to diacids, used for the production of polyamides, polyesters,
lubricants, and also in cosmetics and pharmaceuticals. Among these, azelaic acid [1] is a
commodity with an annual output of 1,000 tons.
The present work propose new methods for its synthesis starting from oleic acid (Scheme 1),
which promise to be more sustainable than the current procedure via ozonolysis.
O
OH
oleic acid
(2a)
(1)
HO
H2O2(60%)
H2WO4 (1:100)
373K
H2O2(60%)
H2WO4 (1:100)
343K
O
OH
OH
9,10-dihydroxystearic acid
(2b)
NaClO
398K
O
HO
OH
O
azelaic acid
+
O
OH
pelargonic acid
Two different approaches have been developed:
- one method (1) adopts a catalytic system consisting of H 2O2/H2WO4 at 373 K for the direct
oxidative cleavage of the double bond of oleic acid.
- the second one (2a) couples a smoother oxidation to 9,10-dihydroxystearic acid with a
subsequent cleavage at room temperature by the action of sodium hypochlorite (2b).
The demarcation points in comparison to what reported in recent reports [1] are (i) a much
lower loading of catalyst, (ii) the absence of phase transfer agents, (iii) a milder work-up.
Keywords: oleic acid, azelaic acid, tungstic acid
* Corresponding author: Roberto Esposito, [email protected]
[1] A. Godard, P. De Caro, S. Thiebaud-Roux, E. Vedrenne, Z. Mouloungui, J. Am. Oil Chem.
Soc. 251 (2013) 133-140 and references there
25
The Comonomer Effect on the CrII/SiO2 Phillips Catalyst:
First Spectroscopic Evidences
C. Barzan1*, S. Bordiga1 and E. Groppo1
1 - University of Turin, Department of Chemistry, Via G. Quarello 15A, 10135 Torino, I
The term „„comonomer effect‟‟ has been widely used with respect to ethylene polymerization
catalysts. It refers to an enhancement in the ethylene polymerization rate when a small amount
of α-olefin comonomer is introduced into the reactor. This phenomenon is curious since olefins
incorporate into the polymer chains with a rate 1-2 orders of magnitude slower than ethylene.
The comonomer effect has been widely studied on Ziegler and metallocenes catalysts. [1, 2]
Recently McDaniel [3] carefully analyzed all possible explanations of this effect also on the
Cr/SiO2 Phillips catalyst, summarizing them as follows: i) incorporation of branching into
polyethylene enhancing ethylene diffusion through the polymer matrix to the active sites; ii)
faster reduction of the chromate species; iii) enhanced fragmentation of the catalyst due to
incorporation of olefins; iv) activation of the active sites by means of the olefins.
We have studied this phenomenon on a Cr II/SiO2 Phillips catalyst, which displays a strong rate
enhancement upon comonomer addition. A non-polymerization olefin, cyclohexene, was used
as “comonomer” to permit to obtain ethylene and olefin homopolymers (polyethylene,
polypropylene and poly-1-hexene) without the incorporation of the comonomer itself. In this
way we removed the effect of the enhanced polymerization activity due to monomer diffusion
into the polymer (point i). We used aerosil as support, in order to avoid fragmentation and
porosity effects (point ii). Using a reduced Cr II/SiO2 catalyst strikes out also the variable of
reducing the oxidized Cr sites (point iii). Moreover, we observed an enhancement from 3 to 6
times higher in ethylene, propylene and 1-hexene homopolymerizations on the Cr II/SiO2
catalyst when it is in presence of cyclohexene. Herein, we show the first spectroscopic
evidences that cyclohexene occupies a coordination vacancy on bare Cr II species and favors
monomer insertion, enhancing the polymerization activity. The use of transmission FT-IR and
Diffuse Reflectance UV-Vis spectroscopies revealed that all CrII sites are in strong interaction
with cyclohexene at room temperature. Moreover, thanks to the use of deuterated ethylene it
was possible to reveal that during ethylene polymerization, cyclohexene is removed from the Cr
active species. We concluded that the enhancement of olefin polymerization rates on the
CrII/SiO2 caused by cyclohexene is due to a molecular rearrangement that extracts the Cr II sites
from the silica surface, making them more available for olefin insertion.
Keywords: Comonomer Effect, Reduced
Polymerization, Rate Enhancement.
Phillips
Catalyst,
Cyclohexene,
Ethylene
*Corresponding author: Caterina Barzan, e-mail: [email protected]
References
[1]
[2]
[3]
L.A. Novokshonova, and V.A. Zakharov, in: W. Kaminsky, (Ed.), Polyolefins: 50
Years after Ziegler and Natta I: Polyethylene and Polypropylene. 99-134.
J.A.M. Awudza, and P.J.T. Tait, J. Pol. Sci. A Pol Chem 46 (2008) 267-277.
M.P. McDaniel, E.D. Schwerdtfeger, and M.D. Jensen, J. Catal 314 (2014) 109-116.
26
High-pressure photoreactor for CO2
conversion to fuels
Matteo Compagnoni1*,Ilenia Rossetti1, Alberto Villa 1, Carlo Pirola
Gianguido Ramis 2 , Di Wang 3
1
, Laura Prati
1
,
1 - Dip. Chimica, Università degli Studi di Milano, INSTM Unit Milano Università andCNRISTM, via C. Golgi 19, 20133 Milan, Italy
2 - Dip. Ingegneria Chimica, Civile ed Ambientale, Università di Genova and INSTM Unit,P.le
Kennedy 1, 16129 Genoa, Italy
3 - Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344EggensteinLeopoldshafen, Germany
CO2 capture and storage is a fundamental research topic in order to decrease the concentration
of such greenhouse gas. A new and challengingprocedure is the CO 2photoreduction to alcohols
and alkanes in the presence of a semiconductor.Unfortunately, the efficiency of the process is
largely restricted by two factors: 1) the limited solubility of CO 2 in water especially at relatively
high temperature; 2) the inadequate visible light absorption of the UV-active catalysts. In
literature, most of the studies were performed using reactors of different shape and type, but
always working at atmospheric pressure.
In this research, we tested a novel concept of photoreactor developed by our group [1] able to
operate under high pressure (up to 20 bar) and to explore different temperature ranges.Through
this set up we can explore unconventional operating conditions, so overcomingthe key
limitation of CO2 solubility, and increase the operating temperature,thus improvingthe overall
kinetic of the process. Na2SO3 has been employed as inorganic hole scavenger. TiO2loadedwith
Au was chosen as photocatalyst. Different titania polymorphs (rutile, anatase, P25) and metal
loading (0.1%, 0.2%, 0.5%) were chosen, to confirm the effect of the physicochemical
properties of the catalysts on reactivity. The samples were prepared by deposition-precipitation
and characterized by traditional techniques (XRD, BET, TEM, UV) combined with specific in
situ analysis (DRIFTS).
The operating conditions (pressure, temperature, pH, irradiation power) have been varied
allowing the investigation of several possible applications of this reactor. In particular we
focused our attention onthe maximization of gas phase products (H 2and CH4) with respect to
liquid phase organic compounds (mainly methanol and formaldehyde).
Keywords: CO2protoconversion; CO2protoreduction; photoproduction of fuels
* Corresponding author: Matteo Compagnoni, [email protected]
References
[1] I. Rossetti, A. Villa, C. Pirola, L. Prati, G. Ramis, RSC Adv.4 (2014) 28883
27
CFD modeling of novel reactor configurations for catalytic combustion
Valeria Di Sarli1, Paola Sabrina Barbato1, Gianluca Landi1, Almerinda Di Benedetto2*
1 – Istituto di Ricerche sulla Combustione, CNR
2 – Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale,
Università di Napoli Federico II
Catalytic combustion is a route to generate power with low environmental impact and through
an inherently safe operation. Typically, catalytic combustion is carried out in monolithic
reactors. The occurrence of combustion at the catalytic surface poses serious thermal
management issues associated with the possible generation of hot spots and consequent catalyst
aging and/or deactivation, eventually affecting the lifetime of the catalyst itself [1].
Temperature excursions over the catalyst are the result of a complex interplay among fluid
flow, chemical reaction and heat exchange.
To evaluate the evolution of the spatiotemporal temperature profiles, modeling is a powerful
tool [2-3]. Over the last years, the use of computational fluid dynamic (CFD) codes has allowed
to solve the coupling between the fluid flow evolution and the heat produced by reaction.
Through the aid of CFD models, novel catalytic reactor configurations can be explored to
improve the thermal management of the reactor itself. In particular, we have recently developed
two novel reactor configurations for preserving the catalyst from hot-spots. These
configurations, named “hybrid” reactors, are based on the concept of partial coating of the
monolith along axial direction [2] or radial direction [3]. In both cases, the catalyst behaves as
an igniter, combustion being mostly homogeneous and stabilized in the uncoated region of the
monolith. Results of CFD simulations have showed that these configurations allow preserving
the catalyst from hot-spots. From numerical results, the operating maps of the reactors have
been built by varying the most important operative parameters.
This work reviews the results obtained through CFD models and simulations, highlighting the
potential of CFD tools in the design of novel catalytic reactor configurations.
Keywords: Catalytic combustion, Novel reactor configurations, CFD
References
[1] D. G. Norton, E. D. Wetzel, D. G. Vlachos, Ind. Eng. Chem. Res. 45 (2006) 76
[2] A. Di Benedetto, V. Di Sarli, G. Russo, Catalysis Today 147 (2009) S156
[3] A. Di Benedetto, G. Landi, V. Di Sarli, P.S. Barbato, R. Pirone, G. Russo, Catalysis Today
197 (2012) 206
28
Dinuclear Iron(III) Complexes containing Thioether-Triphenolate Ligand: Exceptionally
Active Catalysts for the Coupling of Carbon Dioxide with Epoxides for COCs Production
Francesco Della Monica1*, Antonio Buonerba1, Assunta De Nisi2, Magda Monari2,
Ermanno Luciano1, Stefano Milione1, Alfonso Grassi1, Carmine Capacchione1
1 - Dipartimento di Chimica e Biologia, Università degli Studi di Salerno, via Giovanni Paolo
II 132, 84084 Fisciano (SA), Italy and CIRCC, Interuniversity Consortium Chemical Reactivity
and Catalysis, Via Celso Ulpiani 27, 70126 Bari, Italy.
2 - Dipartimento di Chimica G. Ciamician, Alma Mater Studiorum, Università di Bologna, via
Selmi 2, Bologna, Italy.
Carbon dioxide is a renewable, abundant and costless carbon source. Nevertheless its use is
limited by its low reactivity derived from its great stability. Nowadays the interest toward the
use of CO2 as a carbon feedstock is focusing the scientific community attention, since it offers
an effective alternative for the synthesis of organic structure that are currently derived from
fossil based sources. In this scenario the fully atom-efficient cyclo-addition of carbon dioxide to
epoxides, producing useful cyclic organic carbonate of polycarbonate, it‟s attracting the
attention of both industrial and academic researchers.1
Recently we reported on a new robust and highly active
catalytic system for the selective synthesis of cyclic organic
carbonate, based on a series of thioether-triphenolate ligands
and an abundant, non toxic metal such as iron (see figure).[2]
In this contribution we extensively describe the behavior of this new catalytic system. We
evaluated the effect of the steric and electronic demand of the ligand by changing the
substituent on it. The use of a solvent resulted in a loss of catalytic activity, and the system
results stable enough to work under non-dry conditions and with non purified oxiranes.
Noteworthy we obtained very high values of activity and selectivity in the coupling of carbon
dioxide with glycidol for the synthesis of glycidol carbonate, which is an attractive glycerol
derived product.
Keywords: iron, carbon dioxide, cyclic carbonate
* Corresponding author: Francesco Della Monica, [email protected]
References
[1] C. Martìn, G. Fiorani, A. W. Kleij, ACS Catal. 5 (2015) 1353.
[2] A. Buonerba, A. De Nisi, A. Grassi, S. Milione, C. Capacchione, S. Vagin, B. Rieger, Catal.
Sci. Technol., 5 (2015) 118; A. Buonerba, F. Della Monica, A. De Nisi, E. Luciano, S. Milione,
A. Grassi, C. Capacchione, B. Rieger, Faraday Discuss., (2015), DOI: 10.1039/C5FD00070J.
29
Mimicking Enzymes: Fully Organocatalytic Alkyne Hydration Reaction with a
Supramolecular Self-Assembled Capsule
Giorgio La Sorella*, Giorgio Strukul, Alessandro Scarso
Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari di Venezia, via
Torino 155/B, 30172, Mestre (Ve)(ITALY). Fax: +39-041-2340517; Tel:+39-041-2348575
The synthesis of carbonyl compounds via alkyne hydration historically has been carried out
using high amounts of mineral acid and toxic co-catalysts such as Hg (II).1More recently less
polluting but more expensive Co(III), Ru(II), Pt(II) or Au(I) and Au(III) 2precursors were
introduced.In billions of years Nature has developedenzymes as astonishing catalytic systems
that completely surround substrates and provide cavities to stabilize the transition states of
reactions. Artificial self-assembling supramolecular systems can mimic enzyme'sactivity and
selectivity through thein situ generation of cavities that can host substrate molecules. The
inexpensive self-assembled resorcin[4]arene hexameric capsule is characterized by a large
cavity that has been exploited to either host transition metal catalysts or to directly promote
catalytic reactions. Since the capsule binds efficiently cationic and electron poor species, we
exploited this supramolecular catalyst to stabilize cationic intermediates. In this work we report
about the hydration reaction of aromatic alkynes to the corresponding ketones, which is known
to occur through a cationic vinyl intermediate, carried out in the presence of catalytic amounts
of tetrafluoroboric acid and resorcin[4]arene capsule. The confined space within the cavity
favored the hydration of aryl alkynes with reduced steric hindrance, while lower conversion was
observed with larger substrates.The use of a competitive ammonium salt capable to fill the
capsule cavity caused a drastic drop of the
catalytic activity acting, similarly to what
observed with enzymes, as a competitive
inhibitor.
Keywords:
Hydration,
supramolecular
catalysis,resorcin[4]arene.
Alkynes,
Corresponding author: Giorgio La Sorella,
e-mail: [email protected]
References
[1]a) G. A. Olah, D. Meider, Synthesis, 9 (1978) 671; b) R. J. Thomas, K. N. Campbell, G. F.
Hennion, J. Am. Chem. Soc.,60 (1938) 718.
[2] E. Mizushima, K. Sato, T. Hayashi, M. Tanaka, Angew. Chem. Int. Ed,114 (2002) 4745
30
A New Process for Maleic Anhydride Synthesis from a Renewable Building-Block: The
Gas Phase Oxidehydration of Bio 1-Butanol
G. Pavarelli1, A. Caldarelli1, J. Velasquez1, F Puzzo1*, F. Cavani1,2, J. L. Dubois3
1Università di Bologna,Dipartimento di Chimica Industriale “Toso Montanari”, Viale del
Risorgimento, 4, 40136, Bologna (Italy).
2 CIRCC, Consorzio Interuniversitario Reattività Chimica e Catalisi, Research Unit of
Bologna.
3 Pierre BéniteResearch Center (CRRA), Rue Henri Moissan- BP 63, 69493, Pierre
BéniteCedex, France.
The stringent need for the decrease of greenhouse gases emissions is driving the research to
investigate new processes based on renewable raw materials for the production of fuels and
chemicals. One interesting bio-platform molecule is 1-butanol, which is obtained by
fermentation of biomasses.In this work1 we studied the transformation of 1-butanol, both from
chemically and fermentative sources, into maleic anhydride (MA) by means a one-pot
oxidehydration process. The catalyst used for this transformation was vanadyl pyrophosphate
(VPP) because it shows both acid2 and redox3 properties that are necessary to the process.The
catalytic tests were carried out in a quartz continuous flow reactor, by using the industrial VPP
catalyst supplied by DuPont. Products obtained were butenes, acids, CO x, MA and phthalic
anhydride (PA). The maximum yield of MA and (PA) were respectively 40% and 12%. The
tests allowed to optimize the main parameters of the process, in particular the remarkable
importance of the O2/reactant feed molar ratio was highlighted. In fact, either high or low feed
ratio values favoured the non-selective oxidation of intermediate to COx.
The reaction mechanism was also investigated, by coupling in-situ DRIFT spectroscopy and
reactivity experiments.The reaction network was found to include the dehydration of 1-butanol
to butenes, oxidation to crotonaldehyde and oxidation of the latter to MA.
We studied also the reactivity of several bio-sourced 1-butanol. These experiments showed the
possibility to use these raw material, but after purification, because the impurities presenthad a
detriment effect on catalytic performance, affecting the MA/PAselectivity ratio.
In conclusion, we found that is possible to produce MA and PA by the one-pot oxidehydration
of 1-butanol using a vanadyl pyrophosphate catalyst. However, the nature of impurities in biosourced butanol greatly affected the catalyst performance.
Keywords: Oxidehydration, Bio-1-butanol, Vanadyl Pyrophosphate.
References
[1] G. Pavarelli, J. Velasquez Ochoa, A. Caldarelli, F. Puzzo, F. Cavani, J.L. Dubois,
ChemSusChem, in press.
[2] F. Cavani, F. Trifirò, Appl. Catal. A 157 (1997) 195-221.
[3] F. Cavani, G. Centi, I. Manenti, A. Riva, F.Trifirò, Ind. & Eng. Chem., Product R&D
22(1983) 565-570.
31
The synthesis of nicotinic acid by gas-phase oxidation of -picoline:
an analysis of key catalyst features
Massimiliano Mari*, Fabrizio Cavani, Niklaus Kuenzle, Paul Hanselmann, Margarete
Janssen
Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale
Risorgimento 4, 40136, Bologna
Lonza Ltd, 3930 Visp, Switzerland
Introduction
Nicotinic acid is an important vitamin of B group, with an annual production close to 40,000
tons [1]. It is used in medicine, food industry, agriculture and in production of cosmetics.
Nicotinic acid is synthesized commercially by oxidation of -picoline in liquid phase, carried
out with potassium permanganate, nitric acid or sulfuric acid. In an alternative process it is
produced by hydrolysis of pyridine-3-nitrile which is obtained by ammoxidation of -picoline.
We report here about a study aimed at investigating the reactivity of supported vanadium oxide
catalysts for the direct gas phase oxidation of -picoline with air; this process would be an
environmentally more sustainable process compared to currently used technologies.
Experimental part and results
Catalyst based on V2O5 supported over ZrO2 was prepared by means of the wet impregnation
method, using NH4VO3 as V source. Reactivity experiments were carried out using a
continuous-flow, gas phase reactor; the inlet gaseous feed contained 1 mol% -picoline, 24
mol% steam, 17% O2, remainder N2.
The reaction pattern was found to include direct oxidation of alkylpyridine into nicotinaldehyde
and CO2; the former is then further oxidised into nicotinic acid and at a minor extent to CO 2.
Minor by-products were pyridine, nicotinonitrile, bipyridine and CO. Steam was found to play a
crucial role because it favoured the desorption of products and contributed to keeping the V
surface sites available for the reaction. Steam also contributed to limiting the formation of
catalyst surface overheating due to the strong reaction exothermicity and being responsible for
the decline of nicotinic acid selectivity at high temperature. The role of catalyst acid properties
was also investigated.
Conclusions
The main reaction parameters affecting selectivity of -picoline oxidation to nicotinic acid were
investigated. Key steps in the reaction network were found to be the oxidation to
nicotinaldehyde, precursor for nicotinic acid formation, and the consecutive combustion of the
acid into CO2. The results show the importance of steam and reactants ratio on catalytic
performance.
Keywords: nicotinic acid; -picoline; supported vanadium oxide catalyst
* Corresponding author: Massimiliano Mari, [email protected]
[1] R. Chuck, in “Sustainable Industrial Chemistry”, F. Cavani, G. Centi, S. Perathoner, F.
Trifirò (Eds), Wiley VCH, Weinheim, 2009, p. 541-550.
32
On-board H2 production by partial dehydrogenation of fuels
Stefania Albonettia, Chiara Molinaria Carlo Lucarellib, Angelo Vaccaria,*,
a
Dipartimento di Chimica Industriale “Toso Montanari”, ALMA MATER STUDIORUM Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy
b
Dipartimento di Scienza e Alta Tecnologia, Università dell‟Insubria, via Valleggio 11,22100
Como, Italy
Catalytic partial dehydrogenation (PDH) is new way for on-board H2 production, in particular
for aircraft applications. Weigh, volume and energy requirement are specifics for different
vehicles and represent restrictions for the PDH systems. Thus, it is necessary to develop
catalysts highly active and stabile with time-on-stream. The main deactivation is by coke
formation or poisoning by sulfur. Traditional Pt-Sn/Al2O3 catalysts, highly active, but rapidly
deactivated by sulfur, were tested in PDH of single hydrocarbons, their mixtures and LSK
(kerosene with S-content < 3 ppm) [1,2]. The addiction of Sn produces an important increases
of the catalytic activity, due to the formation of different Pt-Sn alloys avoiding a complete
dehydrogenation of the reactants and limiting the coke formation. Best results were obtained
with 1wt%Pt-1wt%Sn/Al2O3 catalyst (CAT1); reducing the acidity of the support by addiction
of 0.5 wt% of K (CAT2), it was possible to limit the C-formation, increasing the life of the
catalyst of about 10 time.
The reaction/deactivation pathway is strictly correlated to the feed used; cyclic molecules
reacted selectively to H2, while linear/aliphatic molecules are also subjected to cracking and
hydrocracking reactions, reducing the H2 yield and the life time of the catalyst due to the
formation of olefin fragments. Increasing the complexity of the feed, the catalyst shows a rapid
deactivation, with an increase of the order grade of the formed coke. At the same time the
presence of olefins give rise to a further increase of the C-formation, the main factor of the
deactivation for higher acidity (CAT1). The deactivation by coke is mainly reversible by
calcination: by increasing the temperature a greater activity recovery was observed. The
mechanism of coke formation has been defined in terms of reaction pathway and involved
parameters. It was demonstrated that the on-board PDH of LSK is possible and a pilot plant has
been developed and tested.
Keywords: On-board; H2-production; Pt:Sn/Al2O3 catalysts; Acidity; Deactivation; Coke
* Corresponding author:: Angelo Vaccari.
References
1. Lucarelli. C., Albonetti S., Vaccari A., Resini C., Taillades G., Roziere J., Liew K.E.,
Ohnesorge A., Wolff C., Gabellini I., Wails D. Catal. Today 175 (2011) 504-508:
2. Lucarelli. C., Pavarelli G., Molinari C., Albonetti S., Mista W., Di Domenico D., Vaccari A.
Inter. J. Hydr. Energy. 39 (2014) 1336–1349.
33
Process simulation and optimisation of H2 production from bioethanol and its use in fuel
cells
Ilenia Rossetti*,Mauro Torli, Marcello Bos, Matteo Compagnoni, Josè Lasso F.
Università degli Studi di Milano, Dip. di Chimica, via C. Golgi 19, 20133 Milan, Italy
H2 production from bioethanol, coupled to fuel cells raised considerable attention in recent
years. In addition, highly innovative solutions for the production of second generation biofuels
are becoming available, leading to environmentally, ethically and economically sustainable
bioethanol.
The main purpose of this work is to quantify the electric power and thermal energy output, as
well as the overall efficiency of a plant with residential size (5 kWelectrical + 5 kWthermal). In
particular, the system is based on a proton exchange membrane fuel cell (PEMFC), fed with
reformate produced by steam reforming of bioethanol. Reformate purification from CO is
accomplished by a series of water gas shift and methanation reactors. Different tools have been
used, such as Aspen ONETM, MatlabTM, Athena Visual StudioTM for process simulation and
kinetic data analysis. The operational variables chosen for the simulation are taken by an
actually existing unit GH2 -BE- 5000 (Helbio SA), which is being tested by the authors in the
frame of a demonstrative project. Thermodynamic and kinetic input parameters have been
obtained, after proper kinetic modeling of available literature data. Among the different
operating variables considered, the water/ethanol ratio was found particularly relevant to
optimise process yield and its economic sustainability.
A detailed revision of kinetic models available was necessary. Therefore, a kinetic model has
been selected, including 14 elementary steps, 4 of which were proposed as rate determining
ones. This model has been applied by us to a full set of experimental data collected for a
Ni/Al2O3and a Rh(1wt%)MgAl2O4/Al2O3 catalyst. This allowed to represent with good
accuracy the experimental data, validating the proposed model for two different catalytic
systems, and to provide a reliable estimate of the whole set of kinetic parameters needed for the
present simulation and for steam reformer reactor sizing.
The process flowsheet used in the process simulations has been optimized with respect to the
existing experimental unit. For instance, we have redrawn the heating and heat recovery system
in order to allow the use of diluted bioethanol solutions. Process simulation has been
successfully accomplished by ASPEN Plus process simulation and Cost Evaluation
tools.Different system layouts have been tested, trying in particular to optimise the heat
exchange network. The possibility to operate with diluted ethanol solutions has been checked,
opening the way to lighter purification strategies for bioethanol, with decreasing production
cost. Therefore, the water/ethanol feeding ratio was the main parameter varied in process
simulation, in order to check its effect on the operation of the reactors and on power output and
efficiency.
Keywords: Ethanol steam reforming; H2 production; Fuel cell system; Process simulation.
34
Amines formation in the Medium Temperature Water Gas Shift Reaction
R. Faure1, G. Fornasari2, D. Gary1, C. Lucarelli3, C. Molinari2, N. Schiaroli2*, A. Vaccari2
1–Centre de Recherche Claude-Delorme, Air Liquide, BP 126, 78354 Jouy-en-Josas (F)
2–Dipartimento di Chimica Industriale “Toso Montanari”, ALMA MATER STUDIORUM Università di Bologna, Viale Risorgimento 4, 40136 Bologna (I)
3 – Dipartimento di Scienza e Alta Tecnologia, Via Valleggio 9, 22100 Como, (I)
H2 is an important raw material in chemical industry and a promising energy vector [1]. Steam
Reforming (SR) and Water Gas Shift (WGS) integrated process is currently the main source of
H2. In the SR reactor, small amount of NH3 forms from N2 present in natural gas,that in the
WGS step, canform amines [monomethyl (MMA), dimethyl (DMA) or trimethyl (TMA)].
These by-products fully dissolve in the unconverted water, recycled for economicreasons to
pre-reforming reactor, withcokeformation and,consequently,catalystdeactivation [2]. This work
reports the role of the reactionparameters in presence of NH 3 andMeOH(WGS by-products) on
amine formation in the WGSreaction at Medium Temperature (MTS), i.e. in just one step to
decrease the production costs.
The tests were conducted in a bench-scale plant, using two catalysts: i) a homemade Cu/Zn/Al
(20 wt. % Cu) obtained by coprecipitationof a hydrotalcite-type (HT) precursor and following
calcination at 550°C for 6 h; and ii) a widely employed commercial Cu/Zn/Al catalyst (26 wt.%
of Cu). A H2/CO/CH4/CO2dry gas (DG) mixture was fed, controlling the flow by a mass
flowmeter, while NH3 aqueous solution was fed using a HPLC pump. After reaction, the gas
were analyzed on-line using a gas chromatograph, (GC) equipped with two HWD detectors,
while the by-productaqueous solution was analyzed off-line using a GCequipped with a FID.
The operating conditions were: DG: H2/CO/CH4/CO2=72.0/18.8/4.6/4.6 v/v; P= 15-20 bar;
Tout=320-340°C; Steam/Dry Gas ratio (S/DG)=0.30-0.40 v/v; contact time (τ)= 3-6 s; NH3
[molar ratio]= 2∙10-4.Bothcatalystsreached the CO conversion equilibrium values regardless of
the temperature in all reaction conditions investigated. Co-feeding NH3, the reaction parameters
strongly affected the formation of by-products, although only the thermodynamically favored
TMA was detected (>150 ppmwt).Theincrease of P and contact time values favored the
formation of MeOH and amines, while a higher S/DG value played an opposite effect. A
correlation may be hypothesized between presence of MeOH and amine formation, suggesting
that unlike that reported in literature [3], amines may form by reaction of NH3 withthe surface
intermediates in MEOH synthesis.
Acknowledgments
The financial supports from Air Liquide (F) and MIUR (Italy) are gratefully acknowledged.
Keywords:Water Gas Shift, Amines, Pre-reforming, NH3, Methanol, Cu-catalysts.
References
[1] J.N. Armor, Appl. Catal.A176(1999) 159.
[2] K.S. Hayes, Appl.Catal. A221 (2001) 187.
[3] S.V. Gredig, R.A. Koeppel, A.Baiker, Appl. Catal. 162 (1997) 24.
35
Low-T mechanistic analysis of NO oxidation and Standard SCR over Fe- and Cu- zeolite
catalysts by chemical trapping techniques
Tommaso Selleri, Maria Pia Ruggeri, Isabella Nova, Enrico Tronconi *
Laboratory of Catalysis and CatalyticProcesses, Dipartimento di Energia, Politecnico di
Milano,
Via La Masa 34, I-20156, Milano (Italy)
The catalytic mechanism governing the low-T Standard NH3-SCR activity over metal promoted
zeolites is still a matter of discussion. Uncertainties are mostly related to the nature of reaction
intermediates [1]. In the present work, we apply chemical trapping techniques to conclusively
identify the products of the NO oxidative activation over commercial Fe-ZSM-5 and Cu-CHA
catalysts.Transient NO+O2 and NO2 adsorption runs were performed at 120 °C on a mechanical
mixture of either Fe-ZSM-5 or Cu-CHA (22 mg) + BaO/Al2O3 (44 mg) powders, loaded in
quartz microtubular reactor.The trapped intermediates were then identified by i) analyzing their
thermal decomposition products by TPD runs, ii) ex-situ FT-IR analysis of the BaO/Al2O3
phase unloaded and separated from the test reactor mixture, and iii) probing their reactivity with
NH3. Gas phase analysis was provided by a UV analyzer coupled with a mass spectrometer to
detect N2.
Upon feeding NO+O2 to the Fe-ZSM-5 (or Cu-CHA) + BaO/Al2O3 mixture at 120 °C, a slow
dynamic response was observed, indicating adsorption of NOx. After reaching a steady state
NO conversion to NO2 around 10%, NO and O2 were removed from the feed and the T-ramp
was started. During the T-ramp, NO and NO2 simultaneously desorbed in equimolar amounts,
with a maximum around 200°C.These results are in line with the thermal decomposition of Ba
nitrites/HONO [2]. The same experiments were carried out also on the individual components
of the mixture, where no appreciable storage of NOx was observed: this suggests that nitrites
are initially formed on the metal active sites, and then trapped and stabilized on the barium
phase. The interaction between the two phases likely proceeds via gaseous HONO (in
equilibrium with nitrites). Nitrites presence is also confirmed by ex-situ FTIR analyses of the
BaO/Al2O3 phases separated from the physical mixtures after exposure to NO+O 2. In both
cases, several bands are evident (1100, 1220, 1270, 1350 cm-1) which can be assigned to
different nitrite species or to free nitrite ions [3]. Trapped intermediates have shown to react
with NH3 in the low temperature range 120 - 140 °C (temperatures at which nitrates are known
to be not reactive) to give Standard SCR products (N 2 and H2O). Nitrites have been thus
identified as the primary products of the NO oxidative activation over Fe- and Cu-zeolites and
as key intermediates under Standard SCR reaction conditions.Consistently, low-T redox
mechanisms for NO oxidation and Standard SCR has been formulated.
Keywords: NO oxidation, Standard SCR mechanism, zeolites, chemical trapping, nitrites
References
[1] M. P. Ruggeri, T. Selleri, M. Colombo, I. Nova, E. Tronconi, J. Catal.311 (2014) 266.
[2] E. Kaiser, C. Wu,J. Phys. Chem., 81 (1977) 1701.
[3] M. P. Ruggeri, I. Nova, E. Tronconi, Top. Catal., 56 (2013) 109.
36
Nano and micro-TiO2 for the photodegradation of ethanol: experimental data and kinetic
modelling.
C.L. Bianchi1,4, C. Pirola1,4, F. Galli1,4, M. Stucchi1,4, B. Sacchi1,4, S. Morandi2,4, G.
Cerrato2,4, V. Capucci3.
1-Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi 19, 20133 Milano.
2-Università di Torino & NIS Inter-departmental Centre, Torino, Italy.
3-GranitiFiandre SpA, Castellarano (MO), Italy.
4-Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, INSTM,
Via Giusti 9, 50121 Firenze
The pollution abatement is very important nowadays, but the worldwide research needs to
develop new “green” technologies [1]. The TiO2-photodegradation of pollutants is an effective
alternative to the much more expensive advanced oxidation processes (AOPs), as the VOC‟s
degradation is a crucial point in order to improve both air and human health quality [2]. In this
study, two different commercial TiO2 samples were tested in the photodegradation of ethanol,
chosen as model molecule, but also considering it as an important atmospheric pollutant:
ethanol emissions accounted for about 4% of the total VOCs anthropogenic emissions in the
UK in 1993 [3].
From a kinetic point of view, the whole process can be simplified considering a two consecutive
first order reactions mechanism on the catalyst surface, in which the adsorbed ethanol is
converted to acetaldehyde, which is mineralized to carbon dioxide and water (LangmuirHinshelwood mechanism). The experimental data were used for the regression of the
characteristics kinetic parameters. Photocatalytic degradations were conducted in a cylindrical
glass reactor with an ethanol concentration of 400 ppmv; the photon sources were provided by a
500 W UV lamp (Jelosil model HG 500) and the VOC‟s molecules were monitored by a gas
chromatography (Agilent 3000 A microGC). The regression of the adsorption and the kinetic
constants were made using MATLAB software; the simulated results exhibit a good fit for the
test performed using both the micro- and nano-samples. The analysis of the kinetic elaboration
gives us important information about the rate of reaction: it is in general increased if catalysed
by nanometric sample. Nevertheless, the catalytic properties of micro-samples are confirmed. In
particular, considering the degradation of ethanol, the rate of its conversion is not so different
for either nanometric or micrometric samples. The micrometric TiO2, less dangerous and less
expensive with respect to the nanometric P25, is active as photocatalysts, being able to degrade
VOCs into CO2, also if with rate of reaction, and then kinetic constants, lower respect the P25.
The good fitting between experimental and simulated results confirms the assumption of a
consecutive first order reaction mechanism degradation pathway that is not influenced by the
TiO2 crystallites dimension.
Keywords: Ethanol photodegradation, kinetic modelling, micrometric TiO 2, VOC.
* Corresponding author: Federico Galli, [email protected]
References
[1] J. Lyu, L. Zhu, C. Burda, Catal. Today 225 (2014) 24–33.
[2] A. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. C 1 (2000) 1–21.
[3] R.G. Derwent, M.E. Jenkin, S.M. Saunders, Atmos. Environ. 30 (1996) 181–199.
37
Mechanistic Kinetic Modeling of NO Oxidation over Cu-chabazite
Amir Reza Fahami, Isabella Nova, Enrico Tronconi*
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di
Milano, Via La Masa 34, 20156 Milano, Italy
In this work we present the development and validation of a mechanistic kinetic model for NO
oxidation to NO2 over a commercial Cu–chabazite catalyst. Such catalysts are nowadays the
state of the art in NH3-SCR for automotive applications: NO oxidation is generally regarded as
an important step in the SCR-deNOx catalytic chemistry. In line with previous researches [1,2],
a Redox mechanism was proposed and, accordingly, a rate equation was derived from the steps
of the mechanism. Copper dimers (Cu-O-Cu)+2 are regarded as the active sites for the NO
oxidation reaction, consistently with recent literature [3]. The first step of the assumed
mechanism is the oxidative activation of NO on the Cu sites, forming nitrites as surface
intermediates (Cu+2-ONO). In the next step, nitrites decompose resulting in the evolution of
gaseous NO2, leaving reduced Cu sites (Cu+1). This step is believed to be the Rate Determining
Step (RDS) of the NO oxidation mechanism at low temperature. Finally, the reduced sites are
reoxidized by oxygen to form copper dimers again. Blockage of the active sites by water as well
as by nitrates buildup via the reaction between nitrites and NO 2 are taken also into account as
inhibitory steps. A systematic set of steady state kinetic runs was carried out over a commercial
Cu-chabazite SCR catalyst to cover the effects of different operating variables on NO oxidation,
including temperature, NO, O2, H2O and NO2 feed concentrations as well as space velocity. The
rate parameters of the individual steps in the kinetic mechanism were estimated by multiresponse non-linear regression based on the least squares method, using the observed temporal
evolutions of the relevant gaseous species concentrations (NO, NO 2) as experimental responses.
The model responses were generated by integrating in time a transient isothermal pseudohomogeneous plug-flow model of the test microreactor. According to both the experimental and
the fit results, NO has a kinetic order close to one, oxygen has a positive fractional reaction
order, while H2O is associated with a strong inhibition effect on NO oxidation, which is well
predicted by the model thanks to the assumption of water blocking the active sites. NO 2 also
exhibits a strong negative effect on the rate of NO oxidation, as also reported by other
researchers [4]. Again, the coverage of the Cu-sites by nitrates invoked in the proposed
mechanism does a good job in describing such an inhibitory effect. In general, we show that the
predictions of the kinetic model based on our proposed redox mechanism for the NO oxidation
are quantitatively in accordance with experimental data for a variety of conditions. This
mechanistic model seems therefore a step forward towards a better understanding of the SCRdeNOx activity of Cu-chabazite catalysts.
Keywords: ammonia standard SCR, Cu-chabazite, kinetic model, Nitrate, NO oxidation
* Corresponding author: Enrico Tronconi, [email protected]
References
[1] M.P. Ruggeri, et al. J. of Catalysis. 311 (2014) 266
[2] M.P. Ruggeri, I. Nova, E. Tronconi, Top. in Catal. 56 (2013) 109
[3] A.A. Verma, et al. J. of Catalysis. 312 (2014) 179
[4] P.S. Metkar, V. Balakotaiah, M.P. Harold, Catal. Tod. 184 (2012) 115
38
Self-healing materials based on Ru and Ru-functionalized-graphene catalysts
Chiara Costabile*, Annaluisa Mariconda, Alessia Di Nicola, Fabia Grisi, Liberata
Guadagno, Pasquale Longo.
Dipartimento di Chimica e Biologia, Università degli Studi di Salerno, Via Giovanni Paolo II,
132, 84084, Fisciano (SA), Italy.
Self-healing materials represents a crucial tool to overcome the difficulties connected to damage
generated by microcracks in polymers and polymer composites during their service in structural
applications.[1] A self-repair material can be manufactured by the storage of healing agents able
to restore the strength of the materials after damage. Among the self-healing systems, one
specific for aeronautic applications was developed by White et al. and involves a
microencapsulated healing agent and a catalytic chemical trigger within an epoxy matrix [2].
Recently, some of us reported on a self-healing system based on the metathesis polymerization
of 5-ethylidene-2-norbornene (ENB) activated by Hoveyda–Grubbs (HG) first generation
catalyst that showed to work at -50°C maintaining the performance of the current structural
composites and allowing a cure temperature up to 180°C without becoming deactivated [3].
Moreover, HG second generation catalysts with N-heterocyclic carbene backbone substitution
were shown to be highly air and moisture stable both in the solid state and in solution for
extended periods of time [4]. Herein, performances of self-healing systems based on HG
catalysts sketched in figure or HG catalyst-functionalized graphene and ENB as healing agent
are reported. The inclusion of graphene in the self healing systems allows both to introduce a
filler covalently bound to the polymer in the repairing material and to cut down the amount of
the expensive Ru-catalysts.
Keywords: self-healing, metathesis, ruthenium,
* Corresponding author: Chiara Costabile, [email protected]
References
[1] Y. C. Yuan, T. Yin, M. Z. Rong, M. Q. Zhang, Express Polym. Lett. 2 (2008) 238.
[2] S.R. White, N.R. Sottos, P.H. Geubelle, J.S. Moore, M.R. Kessler, S.R. Sriram, E.N. Brown,
S. Viswanathan, Nature 409 (2001) 794.
[3] L. Guadagno, M. Raimondo, C. Naddeo P. Longo, A. Mariconda, Polym. Eng. Sci. 54
(2014) 777.
[4] A. Perfetto, C. Costabile, P. Longo, F. Grisi, Organometallics 33 (2014) 2747.
39
Fabrication of ordered arrays of Pd nanoclusters and PdO nanoparticles
by using self-assembled block copolymers as templates
Anna Malafronte 1*, Claudio De Rosa 1, Finizia Auriemma 1, Rocco Di Girolamo
Massimo Lazzari 2
1
,
1 - Department of Chemical Sciences, University of Naples “Federico II”, via Cintia 80126
Naples, Italy.
2 - Centre for Research in Biological Chemistry and Molecular Materials (CIQUS), University
of Santiago de Compostela, 15782 Santiago de Compostela, Spain.
Palladium (Pd) and palladium oxide (PdO) nanoparticles (NPs) synthesis has gained
considerable interest in the last few decades due to their numerous potential utilizations [1-3].
Systems based on Pd show high activity and selectivity in numerous catalytic processes [2, 3],
like the catalytic formation of C-C bonds, one of the most useful transformations in organic
synthesis [2]. Because sustainable development involves the utilization of reusable catalysts, the
search for new catalytic systems to replace existing homogeneous ones is one important issue
[4]. In this context, the immobilization of NPs on a solid support is an interesting alternative
since the catalyst can be recycled by simple filtration and the atom/ion leaching from the
particles can be minimized. Also, many electronic devices, such as resistors, use compositions
containing palladium. All these applications may be more suitable with NPs in a patterned form
and, since the majority of unique NPs properties are highly microstructure-dependent, to form
Pd and PdO arrays on solid supports with a precise control of nanoparticles dimensions and
spacing is a an important issue.
Here, we report a simple method to fabricate arrays of palladium (Pd) nanoclusters and
palladium oxide (PdO) nanoparticles with tunable dimensions and lateral spacing by using
polystyrene-block-poly(ethylene oxide) copolymers (PS-b-PEO) as both stabilizers for Pd NPs
and templates controlling the distribution of them. The cylindrical self-assembled nanostructure
formed from PS-b-PEO has been used as host for selectively sequestering a nanoparticles
precursor (palladium(II) acetate) in cylindrical domains of PEO. Then, Pd NPs have been
obtained by reduction of the precursor in presence of the BCPs. In this way, nanocomposite thin
films of well-defined morphology based on PS-b-PEO matrices and Pd NPs have been obtained.
Furthermore, PdO NPs of improved stability against aggregation have been obtained on a solid
and conductive support (silicon wafer) by treating the Pd containing films in air at elevated
temperatures. We were able to modulate the dimensions of Pd nanoclusters and PdO NPs and
their inter-distance by using as template two different PS-b-PEO copolymers having different
molecular weights of both PS and PEO blocks.
Keywords: block copolymers, nanoparticles, self-assembly
* Corresponding author: Anna Malafronte, [email protected]
References
[1] C. Langhammer, Z. Yuan, I. Zoric, B. Kasemo, Nano Lett. 6 (2006) 833.
[2] A. Balanta, C. Godard, C. Claver, Chem. Soc. Rev. 40 (2011) 4973.
[3] Y. Ozawa, Y. Tochihara, M. Nagai, S. Omi, Chem. Eng. Sci. 58 (2003) 671.
[4] D. Astruc, F. Lu, J.R. Aranzaes, Angew. Chem. Int. Ed. 44 (2005) 7852.
40
Industrially-scalable encapsulation of flexible, microfluidic and polymeric dye-sensitized
solar cells
Federico Bella*,Andrea Lamberti, Stefano Bianco, Elena Tresso, Claudio Gerbaldi,
Fabrizio Pirri
Politecnico di Torino, Department of Applied Science and Technology (DISAT), Corso Duca
Degli degli Abruzzi 24 – 10129 – Torino (Italy)
One of the possible applications of dye-sensitized solar cells (DSSCs) is the biasing of lowpower portable devices. However some critical issues still have to be faced in view of obtaining
flexible cells, readily adaptable to complex shapes. Until today the best performing DSSCs are
based on a rigid housing with glass/FTO electrodes and the use of a liquid electrolyte is critical
for the possible durability of the device. Therefore, suitable flexible electrodes and polymeric
electrolytes are needed.During recent years we deepened a promising approach for the
fabrication of quasi-solid DSSCs with excellent long-term durability. We thoroughly studied
and characterized the integration of self standing polymeric membranes prepared by free radical
photopolymerization, investigating different polymeric formulations. Very recently, this
electrolytic system was integrated with an innovative design for DSSC photoanode, based on
the use of semitransparent metallic meshes as a support for the sensitized nanostructured
semiconductor [1]. For photoanode fabrication, both the use of TiO 2 nanotubes directly grown
on bendable Ti mesh by anodic oxidation and the deposition of mesoporous layers of TiO 2
nanoparticles were investigated with excellent results. The main advantage of this solution is
the possibility to perform the high temperature sintering process (which is mandatory for a well
performing semiconductor layer with good electron transport properties) before the integration
on the final polymeric housing of the cell.
In this work, two flexible electrodes (a titanium mesh supporting N719-sensitized TiO2
nanotubes by anodic oxidation and a Pt-coated mesh) are embedded in flexible PDMS
substrates obtained by partial crosslink reaction before bonding. PDMS is almost totally
transparent to VIS radiation down to 220 nm, thus it represents a valuable substrate for flexible
DSSCs. Moreover, the two PDMS substrates can be sealed by means of a industrially-scalable
UV-curable siloxane methacrylate, thus avoiding the use of thermoplastic films that would
require pressure and high temperatures. Furthermore, PDMS is well suited for the fabrication of
microfluidic devices [2], so it is possible to create holes and channels for the introduction of
liquid electrolytes in large devices or UV-curable monomers containing different redox couples.
The photovoltaic behavior of the resulting solid DSSCs is exhaustively investigated by
electrical measurements and impedance spectroscopy. Preliminary results are definitely
encouraging since efficiencies as high as 4% are obtained in bended configuration.
Keywords: dye-sensitized solar cells, polymer electrolyte, microfluidic, nanostructures
[1] F. Bella, A. Lamberti, A. Sacco, S. Bianco, A. Chiodoni, R. Bongiovanni, J. Membr.
Sci.470(2014) 125
[2] A. Lamberti, A. Virga, A. Angelici, A. Ricci, E. Descrovi, M. Cocuzza, F. Giorgis, RSC
Adv.5(2015) 4404
41
Fe3O4/MoS2 and MoS2: comparisons based on morphological and electrochemical
evaluations for two innovative materials for supercapacitors. Features and prospects
Alfonso Troisi2*, Maria Sarno
Ciambelli1,2
1,2
, Claudia Cirillo2, Eleonora Ponticorvo1, Paolo
1 - Industrial Engineering Department, University of Salerno, Italy
2-NanoMater Center, University of Salerno, Italy
Electrochemical capacitors (ECs), also called supercapacitors, have received considerable
attention for their use as energy storage devices in high-power applications due to their fast
recharge ability, high power performance, long cycle life and environment-friendly merit.
MoS2 has widely studied for this application, probably for its similar to graphene [1] can be
easy synthesized.
In addition, it has attracted great interest in lithium ion batteries and supercapacitors due to their
unique morphology, excellent mechanical and electrical properties [2].
Has been also found that even Fe3O4, has relevant electrochemical properties [3] unlike what
early studies showed [4].
Here, we have investigated and compared the pseudocapacitive behaviors of MoS2 and
Fe3O4/MoS2 nanostructures; the nanoparticles have been produced through a simple, scalable
and low cost "one-step" chemical methodology, consisting in the thermolysis of a suitable
precursor in an organic solvent in the presence of surfactants.
The as-prepared materials have been extensively characterized structurally and morphologically
by X-Ray Diffraction analysis, Transmission (TEM) and Scanning (SEM) Electron Microscopy,
Raman Spectroscopy, Thermogravimetric Analysis and electrochemically using a PotentiostatGalvanostat.
The analysis indicate that the materials have excellent pseudocapacitance properties; in
particular, the analysis to the potentiostat/galavanostat showed high specific capacitances for
both products.
The nanomaterial constituted by the composite Fe3O4/MoS2 showed a better capacitive behavior
compared with pure MoS2, probably due to the perfect combination of the two materials to
morphological and structural that enhances the electrochemical property.
Keywords: Supercapacitors, Graphene, Fe3O4, MoS2, Fe3O4/MoS2
* Corresponding author: Alfonso Troisi, [email protected]
References
[1] H.S.S. Ramakrishna Matte, A. Gomathi, A.K. Manna, D.J. Late, R. Datta, S.K. Pati,
C.N.R. Rao, Angew. Chem. Int. Ed. 122 (2010) 4153–4162;
[2] D. Merki, X.L. Hu, Energ. Environ. Sci. 4 (2011) 3878–3888;
[3] M. Sarno, C. Cirillo, E. Ponticorvo, P. Ciambelli, Chem. Eng. Trans.43, (2015), 727–732.
[4] Wang G., Zhang L., Zhang J., Chem. Soc. Rev., 41, (2012) 797–828.
42
Photodeposition vs. elettrodeposition of Ni(OH) 2 co-catalyst on hematite electrodes for
water splitting application
F. Malara1*, F. Fabbri2, V. Dal Santo1, R. Psaro1 and A. Naldoni1
1 - CNR-Istituto di Scienze e Tecnologie Molecolari, c/o Dipartimento di Chimica, Via
Venezian, 2, 20133 Milano, ITALY
2 - IMEM-CNR, Parco Area delle Scienze 37/A, 43100 Parma, Italy
Photocatalytic splitting of water has attracted extensive attention since the discovery of the
Fujishima and Honda effect,1 providing a route for storing solar energy in the form of chemical
bonds in hydrogen and oxygen.2 Intensive studies are dedicated to developing of anode material
for oxygen evolution, that represent the bottleneck of the process, and hematite (α-Fe2O3) is one
of the most promising materials. It is naturally abundant, inexpensive and no-toxic material
with a low band gap of 2.1 eV which thus allows for utilizing a significant portion of visible
light in the solar spectrum.3 Furthermore, its conduction band edge is positioned with a
sufficient overpotential for oxidizing water to oxygen.2 Nevertheless, its notoriously short hole
diffusion length,4 ow light penetration depth,5 and poor oxygen evolution reaction kinetics have
limited hematite photoanodes development. To overcome these limitations, research efforts
have focused on hematite nanostructuring, compositional fine tuning by doping and deposition
of oxygen evolutioncatalysts(OEC).3
We report the effects of photodeposition and elettrodeposition of Ni cocatalyst on hematite
electrodes. We found that both techniques produce an increase of water splitting efficiency with
respect to bare hematite, but photodeposition produces more effective results: the enhancement
of maximum photocurrent at 1.23V vs. RHE was of 47%, while the current onset was
anticipated of 150mV. Cyclic voltammetry in dark shows that these two deposition techniques
produce two different kinds of Ni hydroxides that cause the different behavior. In particular we
have a strong reduction of the charge transfer resistance at electrode/electrolyte interface in the
case of photodeposition. By cathodoluminescence (CL) spectroscopy we observed that nickel
deposition induces major changes in the intensity and lineshape of the hematite CL emission, as
compared with the bulk material. Both depositions lead to a quenching of the above band-gap
ligand to metal charge transitions (LMCT), furthermore photodeposition induces a CL intensity
decrease of the hematite optical band-gap emission, probably due to an OH bridge between iron
and nickel atoms.
Keywords: water splitting, hematite, nickel hydroxide, photodeposition
References
[1] Fujishima and K. Honda, Nature, 1972, 238, 37
[2] Kudo and Y. Miseki, Chem. Soc. Rev., 2009, 38, 253
[3] J. A. Seabold and K. S. Choi, Chem. Mater., 2011, 23, 1105
[4] S. H. Baeck, K. S. Choi, T. F. Jaramillo, G. D. Stucky and E. W. McFarland, Adv. Mater.,
2003, 15, 1269 .
[5] I. Cesar, K. Sivula, A. Kay, R. Zboril and M. Graetzel, J. Phys. Chem. C, 2009, 113, 772
43
Insights into freeze casting of geopolymers
E. Papa 1*, V. Medri 1, P. Benito 2, A. Vaccari 2, E. Landi 1
1- CNR-ISTEC, National Research Council of Italy, Institute of Science and Technology for
Ceramics, Via Granarolo 64, 48018, FAENZA, Italy
2- Dipartimento di Chimica Industriale “Toso Montanari” – ALMA MATER STUDIORUM Università di Bologna, Viale Risorgimento 4, 40136 BOLOGNA, Italy
Geopolymers with mesoporous matrices and lamellar macro-porosities were produced for the
first time by freeze casting technique [1]; it consists of freezing an aqueous suspension,
followed by ice sublimation under reduced pressure. The process was applied to a reactive
water based sol-gel system, starting from a mixture of metakaolin and potassium silicate
aqueous solution, without addition of any organic dispersant or binder. The synthesis reaction,
geopolymerization, was triggered through a maturation step without reaching a complete
consolidation in order to promote the simultaneous formation of the intrinsic mesoporosity of
the material [2] combined with the lamellar macroporosity obtained from the process. Water
was mixed to the reacting slurry to induce lamellar ice-growth by unidirectional freezing. The
consolidation was completed during freeze-casting and drying, and was of a chemical type,
avoiding any high-temperature thermal treatment.
Macro- and micro-structure, intrinsic and induced porosity size distribution and specific surface
area were investigated. In details, the hierarchical geopolymers, obtained varying the amount of
water used for the freeze-casting, have a total porosities from 53 to 83%, and a specific surface
areas from 4 to 46 m2 g-1. Broad mesopore BJH distributions were detected between 4 to 100
nm with maxima from 5 to 7 nm, while macropores ranged from 1 to 100 µm were identified by
Hg intrusion porosimetry. Lamellar monoliths, boards and tubes were realized by varying the
process conditions, such as: starting formulations, aging, and the mold shape. Thermal
treatments in the range 700-800°C can be applied to further optimize the pore size distribution
and the mechanical properties.
Keywords: geopolymers, freeze casting, meso- macro-porosity, lamellar porosity
[1] E. Papa, V. Medri, P. Benito, A. Vaccari, S. Bugani, J. Jaroszewicz, W. Swieszkowski, E.
Landi, Micropor Mesopor Mat, doi: 10.1016/j.micromeso.2015.05.043.[2] W.M. Kriven, J.L.
Bell, M. Gordon, Ceram. Trans. 153 (2003) 227-250.
44
New sustainable technology to recover returned concrete
Giorgio Ferrari
Mapei S.p.A., Via Cafiero 22, 20158 – Milano (Italy) - e-mail [email protected]
With an estimated production of 25 billion tons per year, concrete is the most used construction
material in the world. [1]. One of the most abundant waste in ready-mixed plants is returned
concrete, the unset concrete that comes back to the plant in the concrete truck as excess
material. This can be the small amount of concrete leftover at the bottom of the drum, or more
significant quantities not used by the costumer at the construction site. Returned concrete at
ready-mixed plant is about 5% of the overall production in the U.S. [2] and 2% in Japan [3]. In
Europe official data are not available, but a rate of 2% is considered a reasonable estimate in
Western Europe. No information is presently available for China and developing countries. On
the conservative hypothesis of an average rate of returned concrete of 1%, it can be estimated
that about 250 million tons are globally generated every year.
All the current methods to treat returned concrete generate waste to be disposed in the landfill.
In the present paper, a new method based on a new additive that transforms returned concrete
into aggregates for new concrete, is presented. The new technology permits the complete
recycling of returned concrete in an easy way, without any waste production. Furthermore, the
new technology reduces the consumption of natural aggregates, with significant benefits both in
terms of natural resource protection and economic saving.
The new additive is based on high molecular weight linear anionic polyacrylamide and
aluminium compound. When added to returned concrete, the new additive causes the
coagulation of the cement paste around the coarse aggregates, forming a granular material
consisting of a core formed by the original stone aggregates covered by a composite material
made by cement paste, sand and the additive.
Results of life cycle assessment (LCA) demonstrated that the new technology is by far less
impacting than the option of dumping of returned concrete and therefore contributes in reducing
the environmental impact of concrete production at the RMC plant, representing an important
contribution for concrete sustainability.
Keywords: Recycled aggregates, returned concrete, superabsorbent polymer, sustainability
References
[1] WBCSD, July 2009, The cement sustainability initiative: Recycling concrete [on-line].On:
www.wbcsdcement.org [Accessed February 4th, 2015]
[2] Obla, K., Kim, H. and Lobo, C., “Crushed returned concrete as aggregate for new concrete –
Final report”, RMC Research & Education Foundation, 2007
[3] Sato, Y., Oyamada, T. and Hanehara, S., “Applicability of sewage sludge ash (SSA) for
paving material: A study on using SSA as filler for asphalt mixture and base course
material”, Proceedings of the Third International Conference on Sustainable Construction
Materials and Technologies, Kyoto, Japan, 2013
45
Water-based reactive silver ink for flexible polymer solar cells and its interaction with the
polymeric hole-transporting layer
Giovanni Iannaccone 1*, Marja Välimäki 2, Elina Jansson 2, Antti Sunnari 2, Gianni Corso
3
, Andrea Bernardi 3, Marinella Levi 1, Stefano Turri 1, Jukka Hast 2, Gianmarco Griffini1
1 - Department Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di
Milano, Piazza Leonardo da Vinci 32, 20133 Milano,Italy.
2 - VTT Technical Research Centre of Finland, P.O.Box 1100, FI-90570 Oulu, Finland.
3 - ENI S.p.A., Research Center for Renewable Energies & Environment - Istituto Donegani,
Via Giacomo Fauser 4, 28100 Novara, Italy.
Polymer solar cells (PSCs) have attracted considerable attention in the last few decades because
of their intrinsic lightweight, their potential transparency, the possibility to fabricate them on
flexible substrates, and the low-cost production potentially achievable by means of all solution
and large-scale roll-to-roll (R2R) processing [1]. PSCs are characterized by a multilayer
architecture where the photoactive layer is sandwiched between a semitransparent front
electrode and a metal back electrode [2]. The solution-based deposition of the metal back
electrode in inverted PSCs is considered one of the crucial issues towards the upscaling of PSC
technology. In this work, a water-based solution-processable silver ink formulation with low
sintering temperature was successfully employed as precursor for the fabrication of the metallic
back-electrode in flexible inverted PSC devices fabricated using R2R-compatible printing
techniques. In order to investigate the effect of the deposition of such reactive silver ink on the
underlying PSC layers, different back-electrode architectures were investigated and thoroughly
characterized. In addition, the influence of the thickness of the hole-transporting poly(ethylene
dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) buffer layer on the functional
performance of the PSC devices was also investigated.
Results revealed that devices incorporating a silver electrode with multi-finger grid structure
outperformed those equipped with a full-coverage electrode configuration. This effect was
correlated with the amount of silver ink that can penetrate through the PEDOT:PSS layer into
the underlying PSC layers and cause shunting effects. Moreover the thickness of the
PEDOT:PSS layer represents a crucial parameter in order to ensure correct functioning of the
PSC devices.
Keywords: polymer solar cells, roll-to-roll fabrication, silver back-electrode, flexible device,
* Corresponding author: Giovanni Iannaccone, [email protected]
References
[1] F.C. Krebs, T. Tromholt, M. Jørgensen, Nanoscale 2 (2010) 873
[2] B. Kippelen, J.-L. Brédas, Energy Environ. Sci. 2 (2009) 251
46
From organic solvents to water: a more sustainable approach toward industriallyupscalable hybrid solar cells
S. Galliano 1*, F. Bella 2, J. R. Nair 2, G. Viscardi 1, C. Gerbaldi 2, C. Barolo 1
1 – Università degli Studi di Torino, Department of Chemistry and NIS Interdepartmental
Centre, Via P. Giuria 7, 10125 Torino, Italy
2 – Politecnico di Torino, GAME Lab, Department of Applied Science and Technology, Corso
Duca degli Abruzzi 24, 10129 Torino, Italy
Since the discovery of Dye-sensitized Solar Cells (DSCs) [1], the scientific community has
always firmly considered the presence of water in the cell, either in the electrolyte or at the
electrode/electrolyte interface, strongly harmful to photovoltaic performances and long term
stability. However, the idea of creating an efficient, inexpensive and environmental friendly
system based on water is still attractive especially for a large scale diffusion of this technology.
In recent years, an increasing number of research articles has been published in this direction
[2,3]
and new dyes, electrodes and electrolyte components are continuously proposed. Being the
initial purpose of DSCs the construction of an artificial photosynthetic system able to convert
solar light into electricity, the use of water as key component may represent a great step forward
to their widespread diffusion in the market. Indeed, by means of DSCs fabricated with 100%
water-based electrolytes, reduced costs, non-flammability, reduced volatility, improved safety
and environmental compatibility could be easily achieved.
A starting point in this direction is given in this work and few peculiar and unconventional
behaviors, observed in the literature and in our laboratories, are presented for truly water-based
electrolytes. This contribution proposes an investigation on the stability of different classes of
dyes, in a fully aqueous environment, and the effect of different aqueous electrolytes.
Particularly, by means of a multivariate approach (DoE) we were able to study different kinds
of aqueous electrolyte, thoroughly investigating their effect on the photovoltaic performance
and stability of the resulting devices.
Keywords: solar cell, aqueous electrolyte, iodine salts, large-scale plant
* Corresponding author: Simone Galliano, [email protected]
References
[1] B. O‟Regan, M. Grätzel, Nature, 1991, 353, 737-739.
[2] W. Xiang, F. Huang, Y.-B. Cheng, U. Bach, L. Spiccia, Energy Environ. Sci., 2013, 6, 121127.
[3] F. Bella, C. Gerbaldi, C. Barolo, M. Grätzel, Chem. Soc. Rev. 2015, 44 (11), 3431-3473.
47
Innovative printable self-cleaning material for covering photovoltaic cells
V. Sabatini1,2*, G. Soliveri 1, H. Farina1,2, M. A. Ortenzi1,2, G. Di Silvestro1,2
1 – University of Milan, Department of Chemistry, Via Golgi 19, 20133, Milan
2 – CRC Materiali Polimerici (LaMPo), University of Milan, Department of Chemistry
The use of polymeric materials, such as sulfonated Polyethersulfones (SPESs), carrying
sulfonic acid groups directly on the polymeric chain, can be very advantageous in fields when
hydrophilic/hydrophobic properties can be modulated, i.e. photovoltaic applications; moreover,
the use of Ionic Liquids (I.Ls.) combined with SPESs can be a way to create tailor-made
hydrophobic materials for solar cells covering.
In particular SPES, a totally amorphous polymer, is characterized by excellent thermal and UV
resistance, optical features, chemical stability, oxidation resistance, as well as by good
mechanical properties and easy processability, i.e. for the production of films or layers [1].
I.Ls., a class of molten salts, have excellent thermal stability and their physical-chemical
properties can be modulated changing the nature of the cation or anion. Modulating cationic
apolar groups can dramatically influence the tendency of I.L. towards efficient ion packing and,
in turn, its hydrophobic features, e.g. the longer the alkyl chains, the more hydrophobic the salt
[2].
In this work, SPESs with different concentrations of sulfonic acid moiety, expressed as degree
of sulfonation (DS), were successfully synthesized using a sulfonated co-monomer. The wetting
properties of SPES could be modulated by introducing different cationic apolar groups through
a novel ionic exchange reaction between the K+ cation of the sulfonic moiety of SPES and the
cation of an I.Ls..
The hydrophobic properties of SPESs treated with I.Ls. were found to improve with the DS of
sulfonation of SPES, i.e. with the number of K + ions available for substitution by the
hydrophobic I.Ls. cations, obtaining contact angles up to 120° (θ) and so self-cleaning surfaces.
Easy processability of SPES due to its viscosity and surface energy makes it a good material for
the production of films through InkJet printer technology, a very simple and economic
deposition technique [3]. Several techniques were used to characterize the films obtained: Wide
Angle X-Ray Scattering allowed for an indirect study of the SPES structure and dimensional
stability. The thermal properties were characterized by Differential Scanning Calorimetry; the
wettability and the morphology were studied by static contact angle measurement and Scanning
Electron Microscopy.
Keywords: Sulfonated Polyethersulfone; Ionic Liquids; self-cleaning material; printable
material.
References
[1] C. Klaysom, B.P. Ladewig, J. Mater. Sci. 48 (2011) 368
[2] P. Bai, X. Cao, J. Biomater. Sci. Polym. 21 (2010) 1559
[3] K. Bica, K. Gaertner, J. Org. Chem. 31 (2008) 3235
48
Palladium macrocomplexes based on Polymers and Copolymers from renewable
resources.
D. Bandelli1*, L. Rosi1,2, M. Bartoli1, W. Oberhauser3, E. Passaglia4, M. Frediani1
1 - Università degli studi di Firenze, Dipartimento di Chimica “Ugo Schiff”, Via della
Lastruccia 3, S.Fiorentino (Fi)
2 - Consorzio Interuniversitario di Reattività Chimica e Catalisi (CIRCC), Via Celso Ulpiani
27, Bari, Italy
3 - Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), 50019 Sesto Fiorentino,
Italy
4 - Istituto di Chimica dei Composti Organometallici (ICCOM-CNR U.O.S.), 56124 Pisa, Italy
The demand for biocompatible and biodegradable plastics is one of the central point in the
scientific research of the last years. In this context, PLA is one of the most interesting polymer
for different applications, from textile to packaging. Even if PLA is defined as a good
replacement for petroleum plastics, the low values of glass transition (Tg) comprised between
30-60°C determines the low field of applications for this polyester. In the last decades the
research of new polyesters with high T g has moved to the synthesis of some alternatives close to
PLA. Polymandelic acid (PMD) is an interesting alternative to PLA, its synthesis can be
performed with different pathways. Liu et al.[1] and Buchard et al.[2] has reported the synthesis
of this polymer with ring opening polymerization (ROP). We performed the synthesis of high
enantiopure mandelide, with interesting results in the yield and in the enantiopurity of the
sample obtained. The choice to polymerize an high enantiopure sample has determinate the
envelopment of a new pathway of polymerization for the synthesis of homopolymeric PMD. On
the basis of works published by Petrucci et al.[3] we approached the synthesis of block
copolymer of PMD with PLA functionalized with bipyridine. Functionalization with bipyridine
groups is interesting to produce new materials useful for macrocomplexation. On the basis of
the works published by Giachi et al.[4] we have also obtained macrocomplexes of the species
synthetized with Palladium Acetate. In addition to this route we investigate the formation of
Stereocomplex between copolymeric samples synthetized with PLLA and PDLA. Even in this
case we have performed the complexation with Palladium Acetate.
Keywords: Polyesters, Block Copolymer, Stereocomplex, Macrocomplexation.
*Corresponding author: Damiano Bandelli, [email protected]
References
[1] Liu, T.; Simmons, T. L.; Bohnsack, D. A.; Mackay, M. E.; Smith, M. R.; Baker, G. L.
Macromolecules 2007, 40, 6040
[2] Buchard, A.; Carbery, D. R.; Davidson, M. G.; Ivanova, P. K.; Jeffery, B. J.; Kociok‐ Köhn,
G. I.; Lowe, J. P. Angewandte Chemie 2014, 126, 14078.
[3] Petrucci, G.; Oberhauser, W.; Bartoli, M.; Giachi, G.; Frediani, M.; Passaglia, E.; Capozzoli,
L.; Rosi, L. Applied Catalysis A: General 2014, 469, 132.
[4] Giachi, G.; Frediani, M.; Oberhauser, W.; Passaglia, E. Journal of Polymer Science Part A:
Polymer Chemistry 2012, 50, 2725
49
Dual Role of Graphite Oxide Nanofiller in Thermosets Resins
Maria Rosaria Acocella1*, Mario Maggio,1 Gaetano Guerra1
1 – Depatment of Chemistry and Biology, University of Salerno, Via Giovanni Paolo II, 13284084- Fisciano (Salerno)
Nanocomposites with carbon-based fillers have been widely investigated due to unique
properties derived from the extended interface between the polymer matrix and the filler. In
particular, many studies have been focused on GO reinforced nanocomposites showing relevant
improvements of physical and mechanical properties. Recently we reported the dual role of
graphite oxide (GO) in epoxy resin thermosets exerted as catalyst on the reaction between the
epoxy and amine groups of the resin, which leads to higher crosslinking density in milder
conditions, and as filler for the nanocomposite.[1]
The dual role of graphite oxide was further investigated for polyester resins showing the GO
ability to promote the polymerisation reaction from the starting monomers, diethyl fumarate and
ethylene glicole, to give useful prepolymers for the following curing step and filler for the final
thermoset resin. The chemical functionalization of GO during the polymerisation assures a
better dispersion reducing the filler aggregation possible observed for graphite-based fillers.
Keywords: Graphite oxide, catalyst, nanofiller, thermosets
* Corresponding author: Maria Rosaria Acocella. Email: [email protected]
References
[1] M.Mauro, M.R Acocella, C. Esposito Corcione, A. Maffezzoli, G. Guerra Polymer 55
(2014)5612-5615
50
Exceptional activity of MWCNT@Pd/TiO2 nano hybrid catalyst in the photo reforming of
biomass derived alcohols
Michele Melchionna1*, Alessandro Beltram1, Tiziano Montini1, Lucia Nasi2,
Maurizio Prato1 and Paolo Fornasiero 1
1 - Chemistry Department, ICCOM-CNR – Trieste Research Unit and INSTM – University of
Trieste via L. Giorgieri 1, 34127, Trieste, ITALY
2 - CNR-IMEM,Parco Area delle Scienze 37/A,43124 Parma, Italy
Clean and efficient hydrogen production is of interest because, in addition to its current use as
molecule of high industrial relevance for the synthesis of NH 3, oil refining and hydrogenation
reactions, hydrogen is envisioned as the fuel of the future. In particular, hydrogen production
from biomass-derived alchols has attracted great interest because of the potential application in
fuel cells [1]. Inspired by one our previous report [2], we have designed a hierarchical synthetic
approach for the preparation of nanohybrids in which appropriately functionalized multiwalled
carbon nanotubes (MWCNTs) were embedded inside mesoporous layers of TiO 2, which in turn
contained dispersed metal nanoparticles (Pd). As shown by microscopy characterization, the
three components are intimately interfaced and the specific roles of the individual components
are merged to direct hydrogen evolution from biomass-derived alcohols, using both UV light
and solar light as energy source.
Thanks to the careful engineering of the nanohybrids, we show that the as-assembled catalysts
exhibit an outstanding activity towards the production of hydrogen from ethanol and glycerol
under UV light, and also a good activity under irradiation by a solar simulator. Through
identification of by-products formed together with H2, and a set of parallel test experiments, we
could partly identify the mechanism of H2 formation. The presence of nanotubes induces a
specific anatase crystal phase of the TiO2 upon thermal treatment, while concomitantly acting
as electron scavenger that retards recombination rates of the photo-produced charge carriers.
TiO2 is the truly photo-induced initiator, while the small Pd nanoparticles are the truly active
sites where the photoexcited electrons are trapped and the reduction of the protons to hydrogen
occurs.
These catalysts represent a new generation of hybrids that can compete as novel benchmark
catalysts in H2 photo-production.
Keywords: hydrogen, carbon nanotubes, titanium dioxide, photoreforming
* Corresponding author: M. Melchionna, [email protected]
References
[1] a) K. Shimura, H. Yoshida, Energy Environ. Sci. 4 (2011) 2467-2481; b) X. Chen, S. Shen,
L. Guo, S. S. Mao, Chem. Rev. 110 (2010) 6503.
[2] M. Cargnello, M. Grzelczak, B. Rodrıguez-Gonzalez, Z. Syrgiannis, K. Bakhmutsky, V. La
Parola, L. M. Liz-Marzan, R. J. Gorte, M. Prato, P. Fornasiero J. Am. Chem. Soc. 134 (2012)
11760.
51
Synthesis of ordered mesoporous carbon materials through soft-template method and
their characterization for catalytic application
S. Andreoli*, M. V. Solmi, G. Fornasari, S. Albonetti
Università di Bologna, Dipartimento di Chimica Industriale “Toso Montanari”, Viale
Risorgimento 4, 40136, Bologna, Italy
In the recent years, the preparation and the characterization of nanostructured carbon have
reached great attention due to the large field of application of these materials and their attracting
properties, such as electrical and thermal conductivity, mechanical strength and chemical
inertness that conventional material cannot match[1].The nanostructured carbons represent a new
class of catalytic materials which includes also the ordered mesoporous carbon (OMC)
obtained, for example, by a replica method from mesoporous silica or other ordered oxides as
sacrificial templating agent which has to be removed. This work focuses on OMC obtained
from the replica method, more specifically, the soft-template method which involves the selfassembly of hydroxybenzenes with a structure-directing agent (such as a non-ionic triblock
copolymers) organized into a micellular-like structure[2]. Then the cross-linker (the aldehyde) is
added to lock the ordered structure; after the phase separation the carbon polymer is isolated
and carbonized to remove also the structure-directing agent[2]. Here two kind of OMC were
studied: both were obtained from the same carbon precursors (phloroglucinol and glyoxal) and
structure-directing agent (Pluronic F127), but with different synthetic procedure. The first one [2]
was developed in acid environment and the curing treatment made in a oven for long time,
while the second one[3] was in basic environment (created with the presence of amines) and the
curing made in an autoclave for shorter time, obtaining a N-containing monolith. After the
pyrolysis (600 or 850 °C) the carbon based materials were characterized as obtained or
subjected to a series of different oxidative treatment (using HNO 3, H2O2 or N2O) with the aim
to create new functional surface groups. The characterization results, obtained from various
kind of analysis (porosimetric analysis, X-ray diffraction, Raman spectroscopy, TEM, TPD and
TGA analysis), evidenced that the samples got from the acid synthesis showed a better structure
in terms of mesopores and order degree, while, with the basic procedure, less ordered and
microporous structures were obtained. Although all the samples showed high surface area (6001000 m2/g). The pyrolysis temperature played an important role: the higher the temperature the
greater the order of the carbon. The surface chemistry of carbon was strongly influenced by
different oxidative treatments suggesting that HNO3 was the more efficient in obtaining an high
degree of O-containing surface groups such as carboxylic acid, lactone and anhydride. Finally,
the possibility of tuning the properties of carbon, make it suitable for many catalytic
applications.
Keywords: mesoporous carbon, OMC, soft-templating, characterization
* Corresponding author: Sara Andreoli, [email protected]
References
[1] D.S. Su, S. Perathoner, G. Centi, Chem. Rev. 113 (2013) 5782-5816
[2] R.T. Mayes, C. Tsouris, J.O. Kiggans Jr., S.M. Mahurin, D.W. DePaoli, S. Dai, J. Mater. Chem. 20
(2010) 8674-8678
[3] G.P. Hao, W.C. Li, D. Qian, G. H. Wang, W.P. Zhang, T. Zhang, A.Q. Wang, F. Schuth, H. J.
Bongard, A. H. Lu, J. Am. Chem. Soc. 133 (2011) 11378-11388
52
Functional Carbon-Based Materials for Advanced Applications
Candida Milone 1*, Emanuela Mastronardo 1, Marianna Fazio 1, Elpida Piperopoulos 1,
Signorino Galvagno 1
1 – Università di Messina, Dipartimento di Ingegneria Elettronica, Chimica e Ingegneria
industriale (DIECII), Contrada di Dio, 98166 Messina
The increase of energy efficiency and the development of clean energy sources are two of the
main global challenges, whose resolution is fundamental to overcome the ever-growing energy
demand. Due to their well-known unique properties, carbon nanotubes (CNTs) can be applied
for these purposes. In this work different CNT morphologies and different CNT composites are
presented as good candidates as functional carbon materials for advanced applications.
Chemical Vapor Deposition (CVD) of methane on Cobalt-Molybdenum-Magnesium catalyst
leads to the production of sponge like CNTs (Fig. 1a), here suggested as promising hydrogen
tank [1].
Also CNTs-based hybrid materials are here proposed as promising candidates for energy
storage systems: Adsorption Heat Pumps (AHPs) [2] and Chemical Heat Pumps (CHPs) [3]. In
order to overcome the poor thermal conductivity of the zeolite in H 2O/zeolite AHP, SAPO-34 is
hydrothermally synthesized over tetraethylammonium hydroxide (TEAOH) modified CNTs
(Fig. 1b). A novel hybrid material for Mg(OH) 2/H2O CHP is developed by DepositionPrecipitation reaction of Mg(OH)2 nanocrystals over functionalized CNTs (Fig. 1c). The
functionalization treatment not only increases CNTs hydrophilic character, but it also enhances
the compatibility between the two components. It is experimentally demonstrated that the
presence of the carbonaceous support improves the heat transfer properties of the storage
medium, thus increasing the overall efficiency of the system.
a
b
c
Fig. 1 “SEM analysis of investigated functional carbon-based materials
Keywords: carbon nanotubes, hydrogen storage, adsorption and chemical heat pumps,
* Corresponding author: Candida Milone, [email protected]
References
[1] B. Assfour, S. Leoni, G. Seifert, I.A. Baburin, Adv. Mater. 23 (2011) 1237
[2] J. Jänchen, D. Ackermann, E. Weiler, H. Stach, W. Brösicke, Thermochim. Acta 434 (2005)
37
[3] Y. Kato, N. Yamashita, K. Kobayashi, Y. Yoshizawa, Appl. Therm. Eng. 16 (1996) 853
53
Development and characterization of silver nano-particles supported on reduced
graphene oxide layers
Marcello Casa 1*, Maria Sarno 1, Nan Wang 2, Johan Liu 2, Paolo Ciambelli 1
1 - Industrial Engineering Department, University of Salerno, Italy
2 - Department of Microtechnology and Nanoscience, Chalmers University of Technology,
Gothenburg, Sweden
The exigency of replacing lead-bearing solders, as interconnection material in microsystem
technology, led to a growing interest in novel electrically conductive adhesives (ECAs). ECAs
have been identified as one of the only environmental-friendly alternatives to the lead in
electronic packaging applications. These adhesives are composite materials made of a
polymeric matrix wich provides mechanical properties and adhesive strength and a metallic
microfiller (usually silver flakes) that supplies thermal and electrical conductivity to the
adhesive. However, commercial conductive adhesives still have lower thermal and electrical
properties compared to lead-bearing solders[1]. This lack of conductivity hinders their wide
application in the system packaging. One of the most effective methods to improve electrical
and thermal conductivity of ECAs is the addition of nano-filler to adhesive filled with
microparticle or the substitution of a part of the microfiller content with nanoparticles [1].
Furthermore, the use of nano material as filler in conductive adhesives not only enhances the
electrical and thermal properties but also enables the ultra-fine pitch capability, while, on the
other hand, lead free solders are not adequate for fine pitch assembly due to their stencil
printing resolution limit [2]. This property can be a great advantage for ECAs, considering that
the electronic microsystems dimensions are shrinking to the nano-domain according to the
Moore‟s law [3]. So far, different kind of nano-materials have been proposed and studied as
additive or alternate filler for ECAs, for example: nano-sized silver particles [4], carbon nanotubes(CNTs) [5], and few layer graphene (FLG) [6]. In this work we have produced and
characterized a novel few layer graphene decorated with silver nanoparticles, to incorporate in a
conductive adhesive as secondary filler [7], with great results in term of conductive adhesive
thermal properties enhancement.
Keywords: graphene, silver, nano-particle, conductive adhesive, packaging
* Corresponding author: Marcello Casa, [email protected]
References
[1] Y. Li and C. P. Wong, Mater. Sci. Eng. R Rep. 51 (2006) 1
[2] Y. Li, K. Moon, and C. P. Wong, Nano-Bio- El. Ph. and MEMS Packaging (2010), 19
[3] G. E. Moore, Electronics 38 (1965) 114
[4] H.-H. Lee, K.-S. Chou, and Z.-W. Shih, Int. J. Adhes. Adhes. 25 (2005) 437
[5] J. Li and J. K. Lumpp, 2006 IEEE Aerospace Conference (2006) 6
[6] K. M. F. Shahil and A. A. Balandin, Nano Lett. 12 (2012) 861
[7] M. Casa, N. Wang, S. Huang, L. Ye, P. Ciambelli, and J. Liu, 2014 15th International
Conference on Electronic Packaging Technology (ICEPT), (2014) 480
54
POSTER ABSTRACTS
55
POLI-01:Isotactic Copolymers of Poly(1-Butene) with 1-Octene from Metallocene
Catalysts: Crystallization Behaviour and Mechanical Properties
Oreste Tarallo,* Claudio De Rosa, Finizia Auriemma, Odda Ruiz de Ballesteros, Rocco
Di Girolamo, Anna Malafronte
Dipartimento di Scienze Chimiche Università di Napoli "Federico II", Complesso
Universitario di Monte S. Angelo, Via Cintia, I-80126 Napoli, Italy.
We report a study of the crystallization and mechanical properties of copolymers of isotactic
poly(1-butene) (iPB) with octene comonomer, prepared with a metallocene catalyst. We found a
surprising result that a high concentration of octene comonomeric units induce crystallization of
form I instead of form II, contrary to what expected from the pioneer studies on copolymers of
iPB from Ziegler-Natta catalysts. In fact, samples with low octene concentrations, up to nearly
6 mol%, crystallize from the melt in form II and octene units stabilize the tetragonal form II,
decelerating or even preventing the usual transformation of form II into the trigonal form I.
Octene concentrations higher than 7 mol% prevent crystallization of the samples from the melt
and the obtained amorphous samples crystallize at room temperature in mixtures of form II and
form I‟. The sample with the highest octene concentration of 11.5 mol% crystallizes
surprisingly from the amorphous phase directly in the pure form I‟. In these samples, form I‟
transforms into form II by stretching which transforms back into form I‟ upon releasing the
tension.
The presence of octene units also affects the mechanical behavior of iPB and produces increase
of flexibility and ductility, and for octene concentration higher than 6-7 mol% induces
unexpected remarkable elastomeric properties. The elastic properties are associated to the
reversible crystal-crystal phase transition between form II and form I occurring during
stretching and when the tension is removed. Elastomeric properties are unusual for iPB and
have never been observed for iPB homopolymers, but have been observed and quite expected
for copolymers of iPB with ethylene. Development of elastomeric properties for copolymer of
iPB with octene is rather unexpected
Keywords: isotactic poly(1-butene), mechanical properties, crystallization
*Corresponding author: Oreste Tarallo, [email protected]
56
POLI-02:Thermoplastic Elastomers from Binary Blends of Syndiotactic Polypropylenes
with Different Stereoregularity
Odda Ruiz de Ballesteros,* Claudio De Rosa, Finizia Auriemma, Rocco Di Girolamo,
Anna Malafronte
Dipartimento di Scienze Chimiche, Università di Napoli “Federico II”, Complesso
Universitario di Monte S. Angelo, Via Cintia 80126 Napoli, Italy.
A study of the structure and properties of binary blends of syndiotactic polypropylene (sPP)
having different degrees of stereoregularity and synthesized by different metallocene catalysts,
is reported. Three series of binary blends have been prepared by mixing a more stereoregular
and crystalline sample sPP1, with concentration of fully syndiotactic pentads rrrr of 78%, with
low stereoregular and poorly crystalline samples samPP1 and samPP2 having [rrrr] = 54.6 and
45.8%, respectively, and a nearly atactic fully amorphous sample amPP with [rrrr] = 26.5%.
All blends show outstanding elastomeric properties with rigidity and tensile strength that can be
tailored by opportunely changing the stereoregularity of the components and blend composition.
A continuous change of properties with composition is observed, from those of high-modulus
thermoplastic elastomers for blends having high concentration of the most syndiotactic sample
sPP1, to those of low-strength elastomers for blends with high content of the less syndiotactic
component.
Keywords: syndiotactic polypropylene, elastomeric properties, polymer blends
* Corresponding author: Odda Ruiz de Ballesteros, [email protected]
57
POLI-03:Crystal Structure of Isotactic Poly((R,S)3-Methyl-1-Pentene).
Chiara Santillo,* Claudio De Rosa, Finizia Auriemma, Rocco Di Girolamo
Dipartimento di Scienze Chimiche, Università degli Studi di Napoli “Federico II”, Complesso
Monte S.Angelo, Via Cinthia, 80126 Napoli, Italia.
The synthesis and the crystal structure of isotactic poly((R,S)-3-methyl-1-pentene)
(iP(R,S)3MP) are presented. The synthetic strategy consists in the preparation of 1,2-poly(E-3methyl-1,3-pentadiene) using a new catalyst based on a cobalt phosphine complex and
successive hydrogenation reaction of the polydiene with p-toluenesulfonyl hydrazide.1 This
procedure has allowed for the preparation of a purely random copolymer of the two
enantiomeric (R) and (S)-3-methyl-1-pentene monomers. The crystal structure of iP(R,S)3MP
has been determined by analysis of the X-ray powder and fiber diffraction patterns and
conformational and packing energy calculations. Chains in 4/1 helical conformation are packed
in a monoclinic unit cell with parameters a = 10.02 Å, b = 18.48 Å, c = 6.87 Å and  = 109.9°
according to the space group P21/b. In the crystals chain stretches of monomeric units with
prevailing S configuration tend to assume a right-handed 4/1 helical conformation whereas
chain stretches of monomeric units with prevailing R configuration tend to assume a lefthanded 4/1 helical conformation. High degree of disorder is present in the crystals due to the
random enchainment of the enantiomeric R and S monomeric units, conformational disorder of
the side chains and packing disorder. Packing disorder originates from the random substitution
of helices of opposite helical handedness that are also anticlined. The crystal structure of
iP(R,S)3MP represents the first example of substitution type disorder in isotactic polymers
between anticlined chains that are also enantiomorphous. The packing scheme in iP(R,S)3MP is
also an example of the impact of the chain-folding scheme on chirality and directionality of
helices in the unit cell and of the impact of the presence of true chiral carbon atoms in the
monomeric unit or compensation of chirality due to the random enchainment of both
enantiomeric monomers on the crystal packing of polyolefins. In fact, whereas the pure chiral
isotactic poly((S)-3-methyl-1-pentene) crystallizes in a chiral tetragonal unit cell,2 the random
achiral copolymer poly((R,S)-3-methyl-1-pentene) crystallizes in a monoclinic unit cell with
breaking of the crystal symmetry.
Keywords: Isotactic Poly((R,S)3-Methyl-1-Pentene), crystal structure, chirality.
* Corresponding author: Chiara Santillo, [email protected].
References
[1]
G. Ricci, G. Leone, A. Boglia, F. Bertini, A. C. Boccia, L. Zetta, Macromolecules 42
(2009) 3048. H. J. Harwood, D. B. Russel, J. J. A. Verthe, J. Zymonas Die Makromol. Chem.
163 (1973) 1.
[2]
V. Petraccone, P. Ganis, P. Corradini, G. Montagnoli, Eur. Polym. J. 8 (1972) 99.
58
POLI-04:Structural characterization of isotactic copolymers of propene with 1octadecene from metallocene catalysts
Claudia Cioce,* Claudio De Rosa, Finizia Auriemma, Rocco Di Girolamo, Giovanni
Talarico
Dipartimento di Scienze Chimiche, Università degli Studi di Napoli “Federico II”, Complesso
Monte S.Angelo, Via Cinthia, 80126 Napoli, Italia.
Single site metallocenic catalysts have allowed the synthesis of a very broad range of
new materials, thanks to the possibility of controlling the microstructure of the polymer [1,2].
The best example is the synthesis of poly(propylene) with several tacticities changing only the
structure of the catalyst [3,4]. Moreover, metallocene catalysts can produce copolymers of
polypropylene even with long 1-alkenes comonomers while keeping a tight control over
comonomer distribution along the chain, the degree of incorporation of the comonomer and the
polydispersity of the molecular mass. The study of copolymers is, in general, of interest for both
scientific and industrial points of view since it affords to establish correlations between the
microstructure of the polymer and the final properties and development of new materials with
tailored properties.
In the present work the relationships between the structure and the mechanical
properties of isotactic copolymers of propylene with 1-octadecene (iPPC18) have been studied.
The samples have been prepared with a metallocene catalyst which yields highly stereoregular
copolymers, with a very small concentration of stereodefects and regiodefects. This molecular
property affords an opportunity for studying the effect of comonomeric units on the
polymorphism and on the physical properties of isotactic polypropylene (iPP). Wide Angle Xray diffraction (WAXS) analysis has revealed that iPPC18 copolymers crystallize in the usual α
form for low comonomeric concentrations and in a new mesofase for higher concentrations.
Small Angle X-ray Scattering (SAXS) technique has been used to measure the lamellar
periodicity and the crystalline lamellar thickness of melt-crystallized compression molded
samples. The lamellar periodicity is rather constant in the whole concentration range while the
lamellar thickness decreases with increasing the comonomer concentration. The results of the
mechanical properties have shown a decrease of the Young modulus, of the yield stress and
elongation at break with increasing octadecene concentration. Moreover, the decrease of the
yield stress is almost linear with the lamellar thickness.
Keywords: isotactic polypropylene, branched copolymers, polymorphism, mechanical
properties.
* Corresponding author: Claudia Cioce, [email protected].
References
[1]
W. Kaminsky, A. Laban, Appl. Catalysis A: General 222 (2001) 47.
[2]
J. Kukral, P.Lehmus, T. Feifel, C. Troll, B. Rieger, Organometallics 19 (2000) 3767.
[3]
J.A. Ewen, R.L. Jones, A. Razavi, J.D. Ferrara, J. Am. Chem. Soc. 110 (1988) 6255.
[4]
H.H. Brintzinger, D. Fischer, R. Mulhaupt, B.Rieger, R.M. Waymouth, Angew. Chem.
Int. Ed. Engl. 34 (1995) 1143.
59
POLI-05:The use of novel PLGA-g-PVP amphiphilic copolymers for fabrication of
nanostructured materials.
Giovanna Capuano,1* Paolo Ferruti,1,2 Amedea Manfredi,1 Elisabetta Ranucci,1 Laura
Paltrinieri,3 Chiara Gualandi,3 Maria Letizia Focarete3
1 - Dipartimento di Chimica, Università degli studi di Milano, via Golgi, 19, 20133, Milano,
Italia;
2 - Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, Via
Giusti, 9 50121 Firenze;
3 - Dipartimento di Chimica “G. Ciamician”, Università di Bologna, via Selmi 2, 40126
Bologna, Italia
The aim of this work is to present a one-pot synthetic process leading to poly(lactide-coglycolide)-g-poly(vinylpyrrolidone) (PLGA-g-PVP) copolymers consisting of high molecular
weight PLGA carrying oligomeric PVP side chains. The title copolymers were prepared by
radical polymerization of N-vinylpyrrolidone in the presence of 50:50 PLGA acting as
polymeric chain transfer agent in the absence of solvents. All copolymers were characterized by
1H-NMR (400 MHz), FT-IR, SEC, MALDI-TOF, DSC, TGA and DLS.
Scheme 1. Synthesis of poly(lactide-co-glycolide)-g-poly(vinylpyrrolidone) (PLGA-g-PVP)
copolymers. Multiple PVP grafts are present on a single PLGA chain.
PLGA is a lipophilic biodegradable polymer, whereas PVP is hydrophilic, biocompatible and
also bio-eliminable for molecular weights < 40.000.1,2 Both polymers have been approved for
human use by the U.S. Food and Drug Administration, therefore the PLGA-g-PVP copolymers
are eligible for medical applications. The water-soluble PVP portion imparts amphiphilicity to
the otherwise hydrophobic PLGA, thus modifying its behavior in aqueous systems. In
particular, PLGA-g-PVP samples spontaneously formed nanoparticles when dispersed in water.
These nanoparticles, besides dissolving hydrophobic drugs, for instance antimalarial drugs, in
the inner core, show higher compatibility than native PLGA towards many drugs known to
interact with PVP. In addition, PLGA-g-PVP samples were co-extruded with PLGA to give
nanofibrous meshes with dramatically improved wettability. These nanofibers can be used in
applications involving contact with the body fluids.
Keywords: PLGA-PVP copolymers, nanoparticles, nanofibers
* Corresponding author: Giovanna Capuano; [email protected]
References
[1] J. M. Anderson, M. S. Shive, Advanced Drug Delivery Reviews, 64 (2012) 72.
[2] X. Liu, Y. Xu, Z. Wu, H. Chen, Macromolecular Bioscience, 13 (2013) 147
60
.
POLI-06:Syndiotactic polystyrene fibers with nanoporous crystalline phases for water and
air purification applications
Christophe Daniel,* Paqualmorica Antico, Gaetano Guerra
Dipartimento di Chimica e Biologia, Università degli Studi di Salerno, Via Giovanni Paolo II,
132- 84084 Fisciano (SA), Italy
Syndiotactic polystyrene (s-PS) is able to form co-crystalline phases with several low-molecular
mass guest molecules and, by suitable guest extraction procedures, two nanoporous crystalline
forms named 1 and [Symbol]2 can be obtained. Both crystalline frameworks rapidly absorb
volatile organic molecules (VOCs), even if present in traces in air or water and hence are
promising for applications in chemical separations and molecular sensorics.
It has been observed that both the kinetics and the sorption capacity of s-PS materials with
nanoporous-crystalline phases strongly depend on the sample morphology. 3 In particular
nanoporous-crystalline polymeric aerogels present a high sorption capacity typical of the
nanoporous crystalline phases associated with the high sorption kinetics typical of aerogels. 3
However the aerogel preparation procedure is energetically and environmentally expensive and
thus is not applicable to a large scale industrial production.
In this contribution it will be shown that syndiotactic polystyrene (sPS) fibers with
nanoporous-crystalline forms can been easily prepared by solvent-induced co-crystallization of
melt-spun crystalline fibers. Crystal structure, morphology and sorption properties of organic
molecules (both from vapour phase and diluted aqueous solutions) for nanoporous fibers
prepared by using different solvents have been investigated and it will be shown that the use of
chloroform which is a strong solvent for s-PS, leads to nanoporous fibres with high uptakes of
VOCs and fast sorption kinetics. In particular, the sorption of VOC traces from water can be
even faster than for s-PS nanoporous aerogels. This unexpected phenomenon is due to etching
of the melt-spun fibers that exposes internal fibrils and markedly increases the surface area up
to 165 m2/g. The outstanding sorption properties and the simple preparation processes, easily
scalable at industrial level, make nanoporous-crystalline fibers particularly suitable as sorption
media for removal of VOC from water and air.
Keywords: syndiotactic polystyrene, fibers, nanoporous-crystalline forms, VOC sorption
* Corresponding author: Christophe Daniel, [email protected]
References
[1] C. De Rosa, G. Guerra, V. Petraccone, B. Pirozzi, Macromolecules 30 (1997) 4147
[2] V. Petraccone, O. Ruiz de Ballesteros, O. Tarallo, P. Rizzo, G. Guerra, Chem. Mater. 20
(2008) 3663
[3] C. Daniel, S. Longo, R. Ricciardi, E. Reverchon, G. Guerra, Macromol. Rapid Commun. 34
(2013) 1194
61
POLI-07:Computational Study of Polypropylene melt: effect of stereoregularity on chain
dimension.
Antonio De Nicola
Giuseppe Milano1
1*
, Finizia Auriemma2, Cluadio De Rosa2, Toshihiro Kawakatsu3,
1 – Dipartimento di Chimica e Biologia, Università di Salerno, via Giovanni Paolo II, 84084,
Fisciano (SA), Italy.
2 – Dipartimento di Scienze Chimiche, Università di Napoli “Federico II”, Complesso Monte S.
Angelo, via Cintia, 80126, Napoli, Italy.
3 – Department of Physics, Tohoku University, Aoba, Aramaki, Aoba-ku, Sendai, Miyagi, 9808578, Japan.
The effect of the degree of stereoregularity of syndiotactic polypropylene (sPP) on the
viscoelastic properties have been recently reported by Ahmad 1 and coworkers. In particular,
they observed an increase of the viscoelastic plateau modulus, in the melt state, increasing the
degree of stereoregularity. Moreover, Ahmad reports that the sPP plateau modulus increases
with the rrrr pentad content. This allow to suppose that in spite of the same molecular weight of
the chain, the different content of rrrr pentads significantly changes the chain dimension.
In this work we want to study, using the Molecular Dynamic (MD), the dependence of
chain dimension of sPP at different degree of stereoregularity. In particular, due to the system
size and the high molecular weight of the sPP, the required computational cost, employing a
fully detailed model, results too expensive.
Recently, De Nicola et al.2 proposed a procedure to obtain a well-relaxed polymer melt
structure with a computational cost extremely low respect standard techniques as coarsegraining or reverse mapping strategies. In particular, the procedure, based on the hybrid MDSCF (Self Consistent Field) approach3, employing a soft potential, allows to generate a full
detailed polymer melt structure with structural correlations indistinguishable from ones
obtained by other strategies.
Keywords: molecular dynamic, polypropylene, stereoregularity
References
[1] N. Ahmad, R. Di Girolamo, F. Auriemma, C. De Rosa, N. Grizzuti, Macromolecules 46,
(2013), 7940-7946
[2] A. De Nicola, T. Kawakatsu, G. Milano J. Chem. Theory Comput. 10 (2014) 5651-5667
[3] G. Milano, T. Kawakatsu, J. Chem. Phys. 130 (2009) 214106
62
POLI-08:Mechanistic understanding of polar monomers polymerization
Laura Falivene 1, Lucia Caporaso2 and Luigi Cavallo 1,2
1 - KAUST Catalysts Center, King Abdullah University of Science and Technology (Saudi
Arabia)
2 - Department of Chemistry, University of Salerno (Italy).
The use of “new” catalytic systems working in reactions that were previously known to be
possible only by transition-metal complexes has attracted growing interest. Organocatalysis
using small-molecule organic compounds, such as N-heterocyclic carbenes (NHC), as catalysts
has risen to prominence over the last decade.
Here we summarize our theoretical investigations on the reactivity promoted by NHCs [1] in
the conjugate-addition polymerization of acrylic monomers. Computational studies have been
focused on the formation of the active species, as well as on the mechanism of chain initiation,
growth and termination, see Chart 1a. Related to the field of methacrylates
organopolymerization, we report the detailed mechanism of proton (H)-transfers process
promoted by NHCs. This process has led to a new kind of polymerization, called ProtonTransfer Polymerization (HTP), to convert dimethacrylates into unsaturated polyesters, see
Chart 1b. The current HTP process is promoted by one specific NHC only.[2] Computational
results have brought to light some results that couldn‟t be reached by only experimental efforts
pointing out that the relative formation/stability of open vs spirocycle adducts that can be
formed for the reaction of polar monomers with the initiator (NHC) is the key point for this
polymerization, see Chart 1c.[3] The equilibrium between these species can have a strong
impact on the initiation as well as on the chain growth kinetics. Indeed, during the
polymerization spirocycle species can be formed, driving thermodynamically the reaction
towards certain products more than others. We have used this knowledge to rationalize the
unique behavior of some catalysts and to screen for other NHCs that could possibly promote the
same HTP reaction.
Chart 1
Keywords: polymerization, DFT, mechanism
*Corresponding author: Luigi Cavallo, [email protected]
References
[1]Y. Zhang , G.M. Miyake, M. G. John, L. Falivene, L. Caporaso, L. Cavallo, E. Y.-X. Chen,
J. Am. Chem. Soc. 135 (2013) 17925.
[2] M. Hong, E. Y.-X. Chen, Angew. Chem. 126 (2014) 12094.
[3] L. Falivene, L. Cavallo, Submitted
63
POLI-9:Polymerization and Copolymerization of L-Lactide and ε-Caprolactone promoted
by Monoamidinate Titanium complexes
Rosita Lapenta 1*, Fabia Grisi 1, Mina Mazzeo 1
1 - Dipartimento di Chimica e Biologia, Università degli Studi di Salerno, Via Giovanni Paolo
II - 84084 Fisciano (SA), Italy,
Aliphatic polyesters such as poly(lactide) (PLA) and poly(ε-caprolactone) (PCL) are
biodegradable and biocompatible polymers that represent promising alternatives to the
petrochemical–based plastics. The most efficient synthetic route for preparation of polyesters
with specific properties and controlled microstructures, in terms of molecular weights,
structures of end groups and steroregularity, is the Ring Opening Polymerization (ROP) of the
corresponding cyclic esters promoted by metal catalysts. These include neutral homoleptic
alkoxide species of Lewis-acid metals such as aluminum, tin (II), yttrium [1], and, group 4
metals [2]. A series of titanium trichloroamidinate complexes have been synthesized with two
distinct ligand sets bearing a phenyl or a methyl substituent at the carbon atom of the amidinate
framework [3]. The steric bulk of the substituents at the N-atoms was also varied to assess the
impact of sterics on the catalytic performance in the ring-opening-polymerization (ROP) of
cyclic esters. The titanium complexes revealed to be very active and robust, able to promote the
polymerization of unpurified monomer under industrially attractive melt conditions, without
loss of activity. They also showed different abilities in the copolymerization of ε-CL and Llactide producing polymers ranging from gradient to truly random microstructures depending
on the initiator architecture.
Keywords: titanium trichloroamidinate complexes, ring opening polymerization, cyclic esters.
References
[1] a) J. Wu, T. L. Yu, C. T. Chen, C. C. Lin, Coordin. Chem. Rev. 250 (2006) 602. b) R. H.
Platel, L. M. Hodgon, C. K. Williams, Polym. Rev. 48 (2008) 11.
[2] C. J. Chuck, M. G. Davidson, G. G. du Sart, P. K. Ivanova-Mitseva, G. I. Kociok-Kohn, L.
B. Manton, Inorg. Chem. 52 ( 2013) 10804.
[3] D. Liguori, F. Grisi, I. Sessa, A. Zambelli, Macromol. Chem. Phys. 204 (2003) 1
64
POLI-10:Co-crystallization with low-molecular-mass guest molecules: a common route for
getting uniplanar orientations of polymer crystalline phases even in the absence of
stretching.
Paola Rizzo 1*, Graziella Ianniello 1, Gaetano Guerra 1
1 - Dipartimento di Chimica e Biologia and INSTM Research Unit, Università degli Studi di
Salerno, via Giovanni Paolo II 132, 84084 Fisciano (SA), Italy
In general, for polymeric materials, the effects of orientation on physical properties are strongly
relevant: for instance, the extent to which it is possible to increase stiffness and strength find no
parallel with other materials. 1 Moreover, crystalline phase orientation is particularly relevant
for functional polymeric materials, when the functionality is mainly associated with crystalline
phases, as for conductive 2 or ferroelectric 3 polymers.
Generally for macroscopic semicrystalline polymers, uniplanar orientations are achieved only
as a consequence of (mainly biaxial) mechanical stretching. The easy achievement of uniplanar
orientation, without mechanical stretching, has been observed so far, by co-crystallization of
syndiotactic polystyrene (s-PS) 4 and poly(2,6-dimethyl-1,4-phenylene ether) (PPO) 5 with
different low-molecular-mass guest molecules.
In this communication, we present the possibility to achieve uniplanar orientation, in the
absence of mechanical stretching, for poly(L-lactic acid) (PLLA) 6 i.e. another industrially
relevant semicrystalline polymer, which is able to co-crystallize with many guest molecules. 7
These recently results let us to suggest that polymer co-crystallization could be a general route
for getting uniplanar orientation, without mechanical stretching, in polymeric thick films.
Keywords: Guest induced crystallization, Thick polymeric films, Crystalline phase orientation
* Corresponding author: Prof. Paola Rizzo, email: [email protected]
References
[1] I. M. Ward, In Structured and properties of Oriented Polymers, Chapman & Hall, London,
(1975); Chapter 1, p. 1.
[2] M. Yoshio, T. Kagata, K. Hoshino, T. Mukai, H. Ohno, T. Kato, J.Amer.Chem.Soc. 128
(2006) 5570
[3] Z.Hu, M. Tian, B. Nysten, A.M. Jonas, Nature Mater. 8 (2009) 62
[4] G. Guerra, C. Daniel, P. Rizzo, O. Tarallo, J. Polym. Sci. Polym. Phys. Ed. 50 (2012), 305
[5] P. Rizzo, G. Ianniello, S. Longo, G. Guerra, Macromolecules 46 (2013) 3995
[6] P. Rizzo, G. Ianniello, V. Venditto, O.Tarallo, Macromolecules (2015) submitted
[7] H. Marubayashi, S. Asai, M. Sumita, Macromolecules 45 (2012)1384.
65
POLI-11:Elastomeric properties and stress-induced phase transformations of syndiotactic
poly(propylene-co-eicosene)
Miriam Scoti,* Claudio De Rosa, Finizia Auriemma, Rocco Di Girolamo, Odda Ruiz de
Ballesteros
Dipartimento di Scienze Chimiche, Università di Napoli “Federico II, Complesso di Monte
Sant'Angelo via Cintia, 80126 Napoli, Italy
Abstract
Copolymers of syndiotactic polypropylene (sPP) with other α-olefins are a new class of
thermoplastic elastomers, where crystallinity, Young modulus, mechanical strength and
elasticity can be tailored through choice of type and concentration of the comonomer. In this
communication we report a study of the structure and mechanical properties of copolymers of
syndiotactic polypropylene (sPP) with branched 1-olefins, such as 1-eicosene. The effect of the
presence of long branches on the crystallization behavior and properties of sPP has been
analyzed. The relationships between structure and stress-induced phase transformations and
mechanical properties have been clarified. Incorporation of long branched comonomers allows
decrease of the glass transition temperature and development of interesting elastomeric
properties. The copolymer samples have been synthesized with a syndiospecific Cs metallocene
catalyst in the range of branches concentrations of 1-10 mol%. All samples show good ductility,
high modulus and good elastic properties. Low glass transition temperature is achieved already
for low comonomer concentrations. The polymorphic transformations occurring during
deformation have been studied by recording X-ray diffraction during stretching and relaxation.
In samples with low comonomer content defective crystals of form I partially transform by
stretching into the trans-planar form III of sPP, and the elastic recovery is associated with the
polymorphic transition of the metastable trans-planar form III into the more stable helical form
II and the trans-planar mesomorphic form of sPP that occurs upon releasing the tension. This
transition provides an enthalpic contribution to the elasticity. 1 Samples with high comonomer
concentrations show very low crystallinity and the classic entropic effect, due to the reversible
transition between extended and random coil conformations of the amorphous chains, is mainly
responsible for the elasticity. These copolymers are a new class of crystalline elastomers
characterized by different types of elasticity depending on concentration of the comonomeric
units and crystallinity. The origin of the elastic behavior is mainly enthalpic for copolymers
having low comonomer content and high crystallinity, whereas it is mainly entropic for high
comonomer concentration.
Keywords: Thermoplastic elastomers, enthalpic elasticity, syndiotactic propene copolymers
References
[1] F. Auriemma, C. De Rosa, S. Esposito, G. R. Mitchell, Angew. Chem. Int. Ed., 46 (2007)
4325.
66
CAT-01:Supported Zinc complex for the esterification and transesterification of vegetable
oils
Rosa Turco1*, Francesco Ruffo2, Vincenzo Benessere2, Maria (E) Cucciolito2, Rosa
Vitiello1, Roberto Esposito1, Veronica Papa1, Martino Di Serio1
1-University of Naples Federico II, Dep. of Chemical Sciences, via Cintia, 80126 Napoli, Italy.
2- University of Naples Federico II, Dep. of Chemical Sciences, via Cintia, 80126 Napoli, Italy
And CIRCC .
Biodiesel is a mixture of alkyl esters of fatty acids produced from vegetable oils (FAME) and is
currently considered a viable alternative to fossil fuels. It is conveniently obtained through
simultaneous esterification and trans-esterification of acidic vegetable oils, such as the residues
of urban or industrial manufactures.
Trans-esterification is typically promoted by alkaline catalysts, but one of the limits of this
approach is the neutralization of the catalyst due to the acidity of the system. This often leads to
unsatisfactory results, and therefore the attention has been recently focused on Lewis acids,
which are able to promote both the reactions. It is found, however, that use of these catalysts in
homogeneous phase gives rise to additional problems related to their corrosive action [1].
A solution to this drawback may result from their heterogeneization, which could also help
catalyst separation and recycling. A successful strategy consists in anchoring traditional
homogeneous catalysts on solid supports, according to the principles of the „homogeneous
supported catalysis‟.
In the light of these considerations, this study has selected as the most promising candidates
complexes of Zn(II) decorated with functional groups that allows for the anchorage to a solid
matrix (as SiO2)[2].
Application of the supported complex in the esterification and transesterification of a variety of
oils, both neutral and at different content of acidity, has revealed that the catalyst is active and
can be recycled several times by simple decantation from the reaction mixture.
Keywords: Zinc catalysts, Transesterification, Esterification
* Corresponding author: author 1, [email protected]
References
[1] M. Di Serio, R. Tesser, L. Pengmei, E. Santacesaria, Energy Fuels 22 (2008) 207.
[2] V. Benessere, M.E. Cucciolito, G. Dal Poggetto, M. Di Serio, M. López Granados, F. Ruffo,
A. Vitagliano, R. Vitiello, Catal. Commun 56 (2014) 81.
67
CAT-02:Ru-based catalysts for γ-valerolactone synthesis
V. Russo1*, L. Minieri2, R. Tesser1, A. Aronne2, S. Andini1, M. Di Serio1
1 - University of Naples “Federico II”, Chemical Sciences department, via Cintia, 4, 80126
Napoli, IT.
2 - University of Naples “Federico II”, Chemical Engineering department, Piazzale V. Tecchio,
80125 Napoli, IT.
Every year about 170 billion metric tons of biomass are produced by nature, a huge amount that
can be considered a driving force for the investigation of chemical transformations to produce
valuable products. This fact lead to a great number of experimental investigations in a wide
range of chemical applications by considering different kind of raw materials, such as
polysaccharides (cellulose and starch), mono and disaccharides, vegetable oils, lignin. At this
purpose, the synthesis of γ-valerolactone (GVL), from the gas-liquid hydrogenation of levulinic
acid (LA), obtainable from the cellulose hydrolysis, has been considered.
Concerning the topic, only few papers have been published till now on the possibility to use
heterogeneous catalysts. Moreover, these papers have to be considered only as preliminary
investigation. An important aspect that comes out from literature is that the classical
hydrogenation catalysts, such as Ru/C, seems to work even better in the presence of an acid cocatalyst [1]. The idea is winning but, in order to optimize the process, it could be better to
design a bi-functional catalyst that present both Lewis and Brønsted acid sites in order to favour
both the hydrogenation and the acid catalyzed steps. At this point, it would be possible to
prepare Ru/Si-Nb catalysts. In particular, Aronne et al. in 2008 shown that gel derived niobiumsilicon mixed oxides present both the acidities with different strength depending on the Nb
content [2]. By adding Ruthenium to this system it would be possible also to keep the
hydrogenation power of the system.
The mentioned catalysts have been tested in terms of performances in both LA conversion and
GVL yield, and compared with commercial Ru/C catalyst obtaining encouraging results.
Keywords: Levulinic acid hydrogenation, γ-valerolactone, Ru-based catalysts
* Corresponding author: Vincenzo Russo, e-mail contact [email protected]
References
[1] A.M. Raspolli Galletti, C. Antonetti, V. De Luise, M. Martinelli, Green Chem. 14 (2012)
688
[2] A. Aronne, M. Turco, G. Bagnasco, G. Ramis, E. Santacesaria, M. Di Serio, E. Marenna, M.
Bevilacqua, C. Cammarano, E. Fanelli, Applied Catalysis A: General 347 (2008) 179
68
CAT-03:Synthesis of biolubricants by esterification using new heterogeneous catalysts
R. Vitiello1, R. Tesser1, R. Turco1, V. Russo1, S. Andini1, M. Di Serio1.
1 - University of Naples „‟Federico II‟, Faculty of Science MM.FF.NN., Department of
Chemical Science.
The purpose of this work is to synthesize biolubricants via esterification biolubricants using
new solid acids as catalysts. In the last years the biolubricants have a great interest in the
scientific world and represent an alternative to the petrochemical lubricants thanks to their
properties like the high viscosity index, the high flash point and the low friction coefficient [1,
2]. Another aspect is the reduction of environmental impact of biolubricants, in fact they are
more degradable, less toxic and so less polluting than mineral lubricants. In the esterification
reaction free fatty acids are used as a renewable biomass and as alcohol are used several
polyols. Vegetable oils, however, have some characteristics, particularly poor resistance to high
temperatures, which prevent their use in many areas of lubrication.
Better performances are obtained from esters produced by reaction of fatty acids, derived from
vegetable oils, and monofunctional or polyfunctional alcohols.
Among these excellent performances as lubricants to be used at low temperature are obtained
with the esters of alcohols and acids with long chain.
In addition to the technological performance of esters, another advantage in their use arises
from the possibility that the raw materials are wholly or largely of natural origin (vegetable oils
or animal fats) and their excellent biodegradability.
The performance of the esters depend on their chemical structure and thanks to the possibility to
use alcohols or fatty acids which differ in the molecular weight and / or in functionality (mono,
di, tri, tetra), can be obtained products with specific performance (viscosity, viscosity index,
pour point, wear resistance, biodegradability). For this reason, research on these products
continues and new syntheses are continually proposed.
In this work biolubricants synthesis from vegetable oils through esterification reaction has been
studied. In the experimental tests the vegetable oils are esterified in the presence of acid
catalysts. In particular solid acids based on H 2WO4/SiO2 containing the 10, 20, 30% by wt of
tungstic acid have been used. The purpose is to verify the catalytic activity and the possibility to
reuse the catalysts.
The results obtained for the synthesis of lubricants are encouraging for all the catalyst studied
using both batch reactor and recycle reactor.
Keywords: biolubricants, solid catalysts, esterification.
References
[1] L. R. Rudnick, Synthetics, Mineral Oils, and Bio-lubricants. Chemistry and technology 3,
2005, 54-57.
[2] J. M. Marchetti, A.F. Errazu, Fuel 87, 2008, 3477-3480.
69
CAT-04:One-pot Glycerol Oxidehydration to Acrylic Acid on Hexagonal-TungstenBronze-Derived Structures as Multifunctional Catalysts
C.Bandinelli 1*, A. Chieregato 1,2, M. D. Soriano 2, F. Basile 1, F. Puzzo 1, P. Concepciòn2,
G. Puglia 1, F. Cavani 1, J. M. Lòpez Nieto 2
1 - Dipartimento di Chimica Industriale “Toso Montanari”, ALMA MATER STUDIORUM
Università di Bologna, Viale Risorgimento 4, Bologna, 40136 ,Italy.
2 - Instituto de Tecnología Química, UPV-CSIC, Campus de la Universidad Politécnica de
Valencia, Avda. Los Naranjos s/n; 46022, Valencia, Spain.
Due to its large availability and chemical versatility, along the latest decades glycerol has
become one of the most attractive bio-based platform molecule for the chemical industry [1].
Between the many options that have been taken into account for its upgrading, an interesting
choice is represented by the one-pot glycerol transformation into acrylic acid. The overall
transformation formally includes two reaction steps: (i) the dehydration of glycerol into
acrolein, and (ii) the oxidation of acrolein into acrylic acid. Our research activity focused on the
development of multifunctional catalytic systems able to combine several chemical steps into a
single transformation [2-5]. Suitable catalysts for this process require bi-functional properties:
(i) Brønsted-type acid sites, for the dehydration step, and (ii) redox properties, for the oxidation
reaction. If on one hand the single-step configuration consists in a considerable alternative
option to the two-step process, on the other hand the multifunctional catalyst approach is very
demanding from the catalyst design point of view, since only fine tuning of acid and redox
properties allows to obtain remarkable yields into acrylic acid.
The catalysts developed by our research group consist of multicomponent mixed oxides (W-VO, W-Mo-O, W-V-Nb and W-Mo-V) whose crystalline structure is strictly related to the
hexagonal tungsten bronze (HTB) type phase. They were prepared by means of hydrothermal
synthesis and characterized with various techniques (XRD, XPS, RAMAN, FTIR, N2adsorption, NH3-TPD, TPR and HR-TEM analysis). Reactivity experiments were carried out in
a bench-scale plant equipped with a continuous flow quartz reactor, operating at atmospheric
pressure. Despite HTBs are well-known compounds in material science, they represent a major
novelty in catalysis. Moreover, the multifunctional materials developed by our group consist in
some of the best performing catalysts for the vapour phase glycerol oxidehydration into acrylic
acid [2-5], showing yields into the acid monomer as high as 51%.
Keywords: hexagonal tungsten bronzes, multifunctional catalysis, oxidehydration, glycerol.
References
[1] S. Bagheri, N.M. Julkaply, W.A. Yehye, Renew. and Sust. En. Rev. 41 (2015) 113
[2] M. D. Soriano, P. Concepción, J. M. López Nieto, F. Cavani, S. Guidetti, C. Trevisanut, GreenChem.
13 (2011) 2954
[3] A. Chieregato, F. Basile, P. Concepción, S. Guidetti, G. Liosi, M. D. Soriano, C. Trevisanut, F. Cavani,
J. M. López Nieto, Catal. Today, 197 (2012) 58
[4] A. Chieregato, M. D. Soriano, F. Basile, G. Liosi, P. Concepción, F. Cavani, J. M. López Nieto, Appl.
Catal. B:env. 150-151 (2014) 37
[5] A. Chieregato, M. D. Soriano, E. Garcìa-Gonzàles, G. Puglia, F. Basile , P. Concepción, C. Bandinelli,
J. M. López Nieto, F. Cavani, ChemSusChem, 8 (2015) 398
70
CAT-05:Development of innovative catalysts for methanation of syngas deriving from
biomass gasification
R. Mafessanti*, D Barisano, F. Basile, G. Fornasari, A. Vaccari
Dep. of Industrial Chemistry “Toso Montanari” – ALMA MATER STUDIORUM – University
of Bologna, , V.le Risorgimento 4, 40136 Bologna, Italy
Recently methanation processes have attracted interest in applications such as energy densification from
biomass stream. However, the selectivity of CO methanation to CO2 one is complex to achieve and, in any
case, limited to narrow temperature ranges that are difficult to control for the exothermicity of the reaction.
In the present study, CO methanation has the aim to produce synthetic natural gas (SNG) from gas
obtained by gasification of biomass. The optimization of the reaction conditions of the syngas methanation
is a very important topic in order to avoid reactions that cause the formation of carbonaceous deposits,
responsible of a sudden loss of activity of the catalytic system. Ni/Mg/Al catalyst derived by layer double
hydroxide (LDH-general formula: [M(II)1-x M(III)x (OH)2]x+ (An-x/n) mH2O]) with lower Ni content (due
to their capacity to produce high Ni dispersion thanks to their high compositional flexibility) with respect
to the commercial catalyst, have been prepared and tested; the modification of the M (II)/M(III) ratio (2.5, 3,
4 – Ni content is maintained constant) was used in order to study its effect on the tendency of carbon
formation. Catalytic tests are carried out simulating a feed composition deriving from a biomass
gasification plant. The best operative (T, P, GHSV) and reaction conditions (H 2/CO, CO/CO2 and steam to
carbon (S/C) ratios) are determined, tuning all the parameters involved, in order to obtain the best
compromise that allows high CH4 yields together with a good stability during time-on-stream (i.e. avoid
carbon formation). The samples are characterized before and after reaction through several techniques
such as XRD, TPRO, TGA, SEM-EDS, Raman spectroscopy and porosimetry. The sample which shows
the best compromise between an high activity and a good stability in any operative condition is that
characterized by the highest basicity [M(II)/M(III)=4]. This sample exhibits H2 and CO conversions
decisively high in any test and the CH4 yields are coincident or very close to those calculated at
equilibrium, even after several hours of reaction (30-40 h).
These results are further confirmed from the
characterization analysis carried out on the samples after
reaction (SEM-EDS, Raman and TGA), in virtue of
those is clear how the sample with the lowest M(II)/M(III)
ratio is the most sensitive towards carbon formation. On
the contrary, the amount of carbon on the sample with
the highest basicity is practically zero; Raman spectra
(Fig. 1) do not show any band ascribable to any type of
carbon and it is barely visible also through TGA
analysis (mass loss < 2%).
This project is carried out, and is still carrying out, in
collaboration with ENEA-Trisaia, where the best
catalysts are tested in pilot plant for the scale up of the
process.
Keywords: methanation, Ni/Mg/Al LDH, M(II)/M(III) ratio, carbon formation
*Corresponding author: Rodolfo Mafessanti, [email protected]
71
CAT-06:New tio-resistant catalysts for on-board H2 productuion
Stefania Albonetti a, Carlo Lucarelli b, Chiara Molinari a, Angelo Vaccari a*
a
Dipartimento di Chimica Industriale “Toso Montanari”, ALMA MATER STUDIORUM Università di Bologna, viale Risorgimento 4, 40136 Bologna, Italy
b
Dipartimento di Scienza e Alta Tecnologia, Università dell‟Insubria, via Valleggio 11,22100
Como, Italy
The partial dehydrogenation of hydrocarbons (PDH), such as gasoline or other fuels, is an
emerging idea of increasing interest to produce pure hydrogen to feed fuel cells for on-board
applications. Therefore PDH offers interesting solutions to many problems thanks to its safe its
transport and storage, while being suitable to produce COx-free hydrogen. In this field,
materials containing Pt and Sn supported on acid supports such as alumina are well known
catalysts for the dehydrogenation of hydrocarbons [1]. The above-mentioned catalysts achieve
very good results in terms of activity in hydrocarbon dehydrogenation, but suffer from a very
fast deactivation due to coke formation and sulfur poisoning [2]. With regard to the formation
of carbonaceous compound on catalyst surfaces, many studies are available in literature,
reporting very good results [3]. The challenge is to tailor a new catalytic system able to work in
real conditions and feeding fuels with relatively high sulfur content, such as kerosene, diesel or
jet fuel.
Supported nickel and cobalt phosphides on high surface area silica (Cab-osil) were employed as
catalysts in the dehydrogenation of synthetic hydrocarbon mixtures and jet fuel. The
characterization of these catalysts revealed the presence of Ni 2P and CoP single phases,
respectively, highly dispersed on the support. H 2-TPD curves indicated that the Ni2P/Cab-osil
catalyst desorbed a higher amount of hydrogen than its counterpart CoP/Cab-osil, in spite of the
fact that their surface area and acidity value are very similar. As a result, Ni 2P/Cab-osil was
more active than CoP/Cab-osil in the dehydrogenation of a hydrocarbon mixture (surrogate)
containing 50 ppm of sulfur, achieving 1500 (NL h -1 kgcat-1) of H2 after 24 h of time-on-stream
(tos). However, the selectivity in the C1-C5 alkanes and/or alkenes increased with tos, being
close to 20 % after 24 h. The reduced acidity obtained by doping the catalysts with KOH (0.5
wt.%) led to a slightly lower activity, although the pattern of the selectivity remained almost
constant. A similar behavior was found using bulk Ni 2P catalyst, showing that the reaction
mechanism was controlled by the active phase. The activity was maintained also feeding a
commercial jet fuel , containing 250 ppm of sulfur.
Keywords: H2-production; Phosphide catalysts; Partial dehydrogenation; Coke formation;
Poisoning by sulphur.
References
[1] Y. Okada, E. Sasaki, E. Watanabe, S. Hyodo, H. Nishijima, Int. J. Hydr. Ener. 31 (2006)
1348–1356.
[2] Bartholomew C.H., Appl.Catal. A212 (2001) 17–60.
[3] C. Lucarelli, G. Pavarelli, C. Molinari, S. Albonetti, W. Mista, D. Di Domenico, A. Vaccari,
Int. J. Hydr. Ener. 39 (2014) 1336-1349.
72
CAT-07:Selective reduction of furfural with MgO and Mg/Fe/O using methanol as Htransfer reactant
L. Grazia* , A. Lolli, Y. Zhang, S. Albonetti, F. Cavani.
1
Dipartimento di Chimica Industriale «Toso Montanari», Università di Bologna, V.le
Risorgimento 4, 40136 Bologna, Italia
Biomasses are currently the most promising alternative to fossil resources for the production of
chemicals and fuels from renewables [1]. For example 2-furfural (FAL), which is produced
from the hemicellulose fraction of lignocellulosic biomass, is a key precursor for the synthesis
of derivatives with applications in polymer industry (furfuryl alcohol, FFA) and in fuels
production such as 2-methylfuran (MF).
Nickel and noble metals based catalysts have been reported to be active towards the conversion
of FFA to MF. Nevertheless, the development of a continuous catalytic process, using nonnoble metals, for the production of MF, is an attractive topic in this field and the tuning of a bifunctional catalyst with hydrogenation and de-oxygenation sites would be a good candidate to
achieve this goal. In our previous work, MgO catalyst has been found to be an excellent
catalyst for liquid phase reduction of FAL to FFA using methanol as H-donor [2]. Using highsurface area MgO as easily recoverable and reusable catalyst for furfural reduction, a 100%
yield to furfuryl alcohol was obtained.
Hereby, we report on the gas phase reduction of FAL to FFA and MF. The reaction was carried
out in a continuous reactor using MgO and Mg/Fe/O catalysts.
MgO and Mg/Fe/O samples were prepared by thermal treatment of hydrotalcite-like precursors.
Catalytic tests were carried out by vaporization of methanol and furfural (molar ratio 10/1) in
N2 flow; gas fed composition was the following (in molar fraction): furfural 5%, methanol 50%,
nitrogen 45%.
Pure MgO was demonstrated to reduce furfural to the corresponding unsaturated alcohol at low
reaction temperature (lower than 350°C), allowing the selective H-transfer from methanol to the
substrate. 2-metyl furan formation, associated with the partial rearrangement of furan ring to
ciclopentanones, was instead observed at higher temperatures.
On the contrary products distribution obtained with the Mg/Fe/O system was significantly
different, and 2-methylfuran formation was favoured when the reaction was carried out between
300 and 400°C. In this range of temperature, tuning the reaction conditions, 2-metyl furan was
produced with very high yield. Nevertheless, the iron presence in the system can also promote
coke formation, leading to a significant deactivation of the catalyst. However, it was possible to
completely regenerate the materials with air treatment at 500°C.
Keywords: furfural, biofuels, hydrogen transfer, methanol
* Corresponding author: Lorenzo Grazia, e-mail: [email protected]
References
[1] N. Chheda, G. W. Huber, J.A. Dumesic, Angew. Chem. Int. Ed. 46 (2007) 7164
[2] T. Pasini, A. Lolli, S. Albonetti, F. Cavani, M. Mella, J. Catal. 317 (2014) 206
73
CAT-08:Direct acid hydrolysis of lignocellulosic and cellulosic biomasses: Zr/P/O system
vs. Nb/P/O system
Mattia Melloni1*, Gherardo Gliozzi1,Gabriele Salvi1, Alessia Mancini1, Fabrizio Cavani1,2,
Anna Maria Raspolli Galletti3, Hilda Gomez Bernal3, Claudia Antonetti3
1-Department of Industrial Chemistry “Toso Montanari”, Alma Mater Studiorum-University of
Bologna, Viale del Risorgimento 4 , 40136, Bologna, Italy
2-Consorzio INSTM, Research Unit of Bologna, Firenze, Italy
3-Department of Chemistry and Industrial Chemistry, University of Pisa, Via Moruzzi 3, 56124,
Pisa, Italy
The conversion of lignocellulosic biomass into valuable chemicals is a strategic issue within the
framework of the biorefinery concept. The starting point of the transformation chain is the
deconstruction of the lignocellulose and depolymerization of the hemicellulose and cellulose to
give monosaccharides, or even transform sugars into other valuable bio-based building blocks.
Difficulties derive from both the resistant lignin sheath and the tight packing of cellulose
chains.
Therefore, it was decided to evaluate the catalytic performances of different metallic phosphate
systems in the heterogeneous catalytic process of direct acid hydrolysis of untreated softwood
dust and ball-milled microcrystalline cellulose[1]: in particular, we have studied Zr/P/O and
Nb/P/O systems. From the tests conducted on both lignocellulose and ball-milled
microcrystalline cellulose, it is possible to observe that the two systems allow similar
conversion of the lignocellulosic biomass: however, while the ZrPO system is active both in the
conversion of cellulosic and hemicellulosic fractions, the NbPO system is active mainly in the
conversion of latter fraction. The ZrPO system shows a higher yield in monosaccharides
(especially in glucose), whereas NbPO system presents a higher activity in the formation of
successive products (5-hydroxymethylfurfural, furfural and levulinic acid).
When microwave irradiation was adopted instead of the traditional heating, a significant
shortening of the reaction time was reached with similar selectivity results, thus confirming the
beneficial role of MW irradiation on biomass hydrothermal conversion.
The differences of catalytic performances between the two metal phosphate catalysts can be
explained by invoking both the different total concentration and type of acid sites [2]: we
evaluated the total concentration of acid sites by means of ammonia TPD and the type of acidity
(Brønsted/Lewis acid site ratio) by means of FT-IR adsorption of pyridine [3].
It is possible to conclude that: the ZrPO system has a higher concentration of total acid sites,
that results into a higher conversion of the biomass, in particular of the cellulosic fraction;
instead, the NbPO system presents a higher Brønsted/Lewis acid sites ratio, that reduces the
production of monosaccharides in favor of successive decomposition products.
Keywords: biomass conversion, lignocellulose and cellulose, metallic phosphate.
References
[1] Gliozzi G., Innorta A., Mancini A., Bortolo R., Perego C., Ricci M., Cavani F., Applied Catalysis B:
Enviromental 145 (2014) 24-33.
[2] Weingarten R., Kim Y.T., Tompsett G.A., Fernàndez A., Han K.S., Hagaman E.W., Conner Jr.
Wm.C., Dumesic J.A., Huber G.W., Journal of Catalysis 304 (2013) 123-124.
[3] Busca G., Physical Chemistry Chemical Physics 1 (1999) 723-736.
74
CAT-09:Synthesis of isoprene trough C4 – C1 coupling: substituting formaldehyde
with methanol, an investigation over the reaction mechanism
Andrea Malmusi*, Matteo Dellapasqua and Fabrizio Cavani
Università di Bologna, Dipartimento di Chimica Industriale “Toso Montanari”, Viale
Risorgimento 4, 40136, Bologna
Introduction
2-Methyl-1,3-butadiene, commonly named isoprene (IPE), is an important monomer for rubber
production. One process used for to IPE exploits the Prins reaction between isobutene and
formaldehyde over acid catalysts1. The main drawback of this process is the use of
formaldehyde, which is carcinogenic and can lead to catalyst deactivation. We investigated an
alternative route2,3 to isoprene: methanol-isobutene coupling; this work deals with an
investigation on the coupling reaction scheme over an Al/P/O-based catalyst.
Experimental part and results
Amorphous Al/P/O catalyst (150 m2/g) was synthesized by a co-precipitation method 1
followed by drying and calcination at 550°C/3h. The catalyst was tested in a gas-phase reactor
at 400°C, with a methanol/isobutene feed ratio 1/6, varying contact time. Some experiments,
aimed at the investigation of the role of reaction products, were carried out by feeding either
dimethylether (DME) and isobutene or IPE only. By combining all experimental results it was
possible to draw the reaction scheme (figure 1). We found that isobutene reacts directly with
methanol to IPE, together with 2-methylbutenes and DME. IPE also underwent a consecutive
decomposition to either the retro-Prins products or to 2-methylbutenes.
Fig. 1: Simplified reaction scheme of isobutene-methanol coupling to isoprene.
Conclusions
The mechanism of the reaction between isobutene and methanol on Al/P/O catalyst was
elucidated. Further investigations on the parameters affecting catalytic performance can lead
to an improvement in isoprene yield.
Keywords: isoprene, AlPO, methanol, isobutene
* Corresponding author: Andrea Malmusi, [email protected]
[1] V. L. Sushckevic et al. Applied Catalysis A: General 441-442 (2012) 21-29
[2] W. Yoshihiro et al. USP 3621072, Sumitomo Chemical Company (1967)
[3] P. Y. Gokhberg et al. USP 4147736 (1977)
75
CAT-10:A new strategy for the obtainment of fluorinated resins as catalytic support
Chiara Dalla Valle*, Marco Zecca, Paolo Centomo
Università degli Studi di Padova, Dipartimento di Scienze Chimiche, via Marzolo 1, 35131
Padova
Cross-linked functional polymers (CFPs), also known as functional resins, are widely used in
heterogeneous catalysis, especially in acid catalyzed reactions. Furthermore, thanks to their
ability to bind a metal precursor and control the growth of metal nanoparticles, these materials
can be used also in supported metal catalysis. [1]
These materials can be conveniently functionalized to design their catalytic properties. In the
present work a novel and promising type of functionalization of polystyrene-divinyl benzene
resins is presented, based on the Friedel-Crafts acylation with perfluoroacylic chains. A gel-type
resin (with a DVB content of 2% wt) was successfully acylated with perfluorobutyryl chloride
obtaining a material with approximately 19% of acylated aromatic rings. A novel kind of polydivinylbenzene, prepared under solvothermal-like conditions and featured by high surface area
(up to 1100 cm3/g) and pore volume (2 ml/g), mainly produced by meso- and macropores (4-50
nm) [2], was also functionalized in this way leading to the acylation of 12% of the aromatic
rings.
The acylated resins have been sulfonated with sulfuric acid to obtain the corresponding
fluorinated cation-exchange resins. These acidic catalysts, featured by the co-presence of
lipophilic and hydrophilic moieties, appear interesting to promote reactions between reagents
with very different polarity. [3] Moreover, it is well known that gases like hydrogen and oxygen
are relatively very soluble in fluorinated solvents. [4] Accordingly, in a supported metal
catalysts the accumulation of gases close to the active metal should be favoured if the support is
a flourinated resin. The performance of sulfonated, fluoroacylated resins as either catalysts in
the reaction of esterification of stearic acid with methanol or supports for metallic catalysts in
the direct synthesis of H2O2 are reported as illustrative examples of the potential benefits
achieved with these materials.
Keywords: resin, catalysis, fluorinated support
Corresponding author: *[email protected]
References
[1] M. Zecca, P. Centomo, B. Corain, in: Metal Nanoclusters in Catalysis and Materials Science
(B. Corain, G. Schmid, N. Toshima, eds.), Elsevier, Amsterdam (2008) 201–232
[2] S. Sterchele at al, Microporous and Mesoporous Materials, 2014 (185) 26-29
[3] P. Centomo et al, Topics in Catalysis 2013 (56) 611-617
[4] J. G. Riess, M. Le Blanc, Pure & Appl.Chem. 1982 (54) 2383-2406
76
CAT-11:Transesterification of castor oil with trimethylchlorosilane for BioDiesel and αmonochlorohydrin production
Antonella Salvini1*, Marino Malavolti1, Alberto Brandi1, Donatella Giomi1
1 - Department of Chemistry “Ugo Schiff” University of Florence, Via della Lastruccia 3-13,
50019 Sesto Fiorentino (Italy),
BioDiesel (BD) is a well known commodity which is correlated, in a world wide scale
production, with different economic, political, environmental and ethical issues. In particular, in
order to avoid BD production from edible oils many efforts have been made to convert
feedstock such as non-edible oils, exhausted fried oils, oils from microalgae and waste animal
fats into BD. Among non-edible oils, castor oil seems to be a good candidate for BD
production. The transesterification reaction with methanol and ethanol has been studied both
with basic and acid catalysts [1]. Acid catalysis is generally more efficient, probably because of
the higher solubility of castor oil in alcoholic medium, that allows a monophasic reaction.
Recently, a method for producing BD using trimethylchlorosilane (TMSCl) as “mediator” has
been reported [2, 3] and in this process, transesterification and esterification are performed at
the same time. Furthermore, glycerol, obtained as coproduct from BD production, has been
selectively converted in mono- and dichlorohydrins using TMSCl as chlorinating agent and
acetic acid as catalyst [4].
Now, the reaction between castor oil and various alcohols in the presence of TMSCl as acid
mediator has been studied. A facile process provides two remarkable one pot reactions:
transesterification of triglycerides, relevant to BioDiesel production, and chlorination of
glycerol, with formation of α-monochlorohydrin, as predominant product, relevant for industrial
purposes. The reaction conditions have been thoroughly investigated to optimize conversion
and selectivity.
Keywords castor oil, BioDiesel, chlorohydrins, trimethylchlorosilane
* Corresponding author: Antonella Salvini, e-mail: [email protected]
References
[1] S. M. P. Meneghetti, M. R. Meneghetti, C. R. Wolf, E. C. Silva, G. E. S. Lima, L. de Lira
Silva, T. M. Serra, F. Cauduro, L. G. de Oliveira, Energy Fuels 20 (2006) 2262
[2] A. Brandi, A. Salvini, G. Cipriani, D. Giomi and G. Bartolozzi, Patent WO 2011/023712 A1
[3] A. Salvini, D. Giomi, G. Cipriani, G. Bartolozzi, R. Alfini, A. Brandi, RSC Adv. 2 (2012)
4864
[4] D. Giomi, M. Malavolti, O. Piccolo, A. Salvini, A. Brandi, RSC Adv 4 (2014) 46319
77
CAT-12:Green synthesis of ruthenium nanoparticles on magnetic carbon nanostructures
and their use for the selective hydrogenation of nitroaromatics
E. Bertolucci1*, A. M. Raspolli Galletti2, M. R. Axet3, P. Serp3
1- Scuola Normale Superiore, Piazza dei Cavalieri, 7, 56126, Pisa, Italy
2- University of Pisa, Department of Chemistry and Industrial Chemistry, Via Moruzzi 3,
56126, Pisa, Italy
3- University of Toulouse, Laboratoire de Chimie de Coordination composante ENSIACET, 4
allèe Emile Monso, 31030 Toulouse, France
Carbon nanostructures find a wide range of applications in different industrial and technological
fields. In particular their promising electrical, chemical and physical properties could improve
the catalytic activity of metal nanoparticles attached on their surface. However an essential
aspect for practical application of these nanomaterials in catalytic industrial processes is their
recoverability and recycling. For this reason anchoring magnetic nanoparticles on the surface of
carbon nanosupports could be a strategic choice able to guarantee their efficient magnetic
separation from the reaction media. The aim of this work is to propose a new sustainable and
eco-friendly procedure to anchor ruthenium and/or magnetite nanoparticles on the surface of
multiwall carbon nanotubes (CNT) and graphene oxide (GO). This green method is based on
the use of: an alcohol as a solvent and reducing agent, monomode microwave as efficient
heating source, short reaction time, the absence of hazardous reducing and stabilizing agents.
The obtained products were magnetically recovered and then characterized by TEM, ICP-AES,
AES, XRD, SQUID analyses. Fe3O4@CNT, Fe3O4@GO, Ru@(Fe3O4-CNT) and Ru@(Fe3O4GO) systems show a promising narrow size distribution and interesting magnetic behaviour able
to guarantee an easy and efficient magnetic separation from the reaction medium.[1-2]
Furthermore all the catalytic systems were employed in the selective hydrogenation of pchloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN) under mild reaction conditions.The
Ru@CNT, Ru@GO, Ru@(Fe3O4-CNT) and Ru@(Fe3O4-GO) catalysts show 100% of
selectivity and a noteworthy conversion in the first reaction hour. In particular Ru@(Fe 3O4-GO)
shows the best Turnover frequency (328 h-1), followed by the Ru@GO nanocatalyst with 286 h1
. This study opens the way for industrial employ of magnetically recoverable Ru/carbon
nanocatalysts.
Keywords: magnetic graphene oxide, ruthenium nanocatalysts,hydrogenation.
* Corresponding author: Elisa Bertolucci, [email protected]
References:
[1] M. Raspolli Galletti, E. Bertolucci, M. Marracci, B. Tellini, C. Visone, “Characterization of
magnetite nanoparticles,” Instrumentation and Measurement Technology Conference (I2MTC)
Proceedings, 2014 IEEE International (2014) 464.
[2] E. Bertolucci, R. Bacsa, A. Benyounes,[b,c] A. M. Raspolli-Galletti, M. R. Axet, P. Serp,
“Carbon support effect on the catalytic activity of ruthenium-magnetite catalysts for pchloronitrobenzene hydrogenation”, In press ChemCatChem (2015) DOI:
10.1002/cctc.201500364R1
78
CAT-13:Thermal- and Photo-Activation of CrVI/SiO2 Phillips Catalyst with Ethylene:
Operando Spectroscopic Evidences
C. Barzan1*, L. Mino1, A. Piovano1, A. Zecchina1, G. Spoto1, S. Bordiga1 and E. Groppo1
A dominant share of polyethylene production is based on the silica-supported chromium-based
Phillips catalyst (CrVI/SiO2) [2], whose discovery dates from 1954. Although 60 years passed,
the structure at the molecular level and the oxidation state of the species active in ethylene
polymerization are still debated. It is assumed that at temperatures from 80 to 130 °C ethylene
reduces the CrVI species to a lower oxidation state in a first step forming mainly formaldehyde,
and secondly it is polymerized on the so reduced Cr sites. The lack of knowledge in the
structure of the Cr active sites is mainly due to the difficulty in the distinction/separation of the
reduction and the polymerization steps.
In this contribute, we present the investigation of the CrVI species during ethylene reaction using
operando set-ups coupled with highly sensitive spectroscopic techniques such as transmission
FT-IR, Diffuse Reflectance UV-Vis, and XANES (performed at BM23 beamline in Grenoble F-). The reaction between CrVI grafted species and ethylene is promoted not only by heating
(110-130 °C) but also with extremely collimated UV light irradiation (Fig. 1a) and b),
respectively) resulting in slightly different Cr sites. In both cases formaldehyde was primarily
formed, although other ethylene oxidation by-products were detected. The whole set of
spectroscopic results unveils the formation of mainly two different chromium sites.
Figure 1: Part a) shows time-resolved XANES spectra of CrVI/SiO2 (in black) during ethylene reaction at
110 °C (progressive color shading from black to red). Part b) shows the transmission FT-IR and DRUVVis spectra of CrVI/SiO2 catalyst ( black curves) during irradiation under UV light in presence of ethylene
at room temperature (from dark blue to light blue curves).
Keywords: heterogeneous catalysis, ethylene polymerization, Cr-based Phillips catalyst, vibrational and
electronic spectroscopies, operando
* Corresponding author: Caterina Barzan, e-mail: [email protected]
[1]M.P. McDaniel, Adv. Catal., 53 (2010) 123.
[2]J.P. Hogan and R.L. Banks, (1958) U.S. Patent 2, 825, 721
79
CAT-14:Cyclohexene and Methane as Reducing agentsfor CrVI/SiO2 Phillips Catalyst
C. Barzan1*, A. Piovano1, L. Braglia1, M. Botavina1, G. Agostini2, S. Bordiga1 and E.
Groppo1
2 - European Synchrotron Radiation Facility, 6 Rue Jules Horowitz, F-38600 Grenoble, F
Cr-based Phillips catalysts hold more than the 40 % of HDPE and LLDPE world catalytic
production. The polymerization process is based on converting ethylene to polyethylene at 80130 °C; at these temperatures ethylene firstly reduces the surface chromate species to lower
oxidation states in the so called induction period and secondly it is polymerized. Often prereducing reagents are added to CrVI based catalysts in the industrial practice, prior ethylene
injection in the feedstock. The most common reducing agent is CO, which reduces CrVI sites to
highly uncoordinated CrII sites and CO2 at 350 °C (left in Fig.1).
Herein, we present two different reducing agents leading to different Cr reduced species:
a) Methane was chosen because it leads to a catalyst displaying a very high reactivity towards
ethylene [1]. We report how methane reduces chromates at 400 °C leading to CrII and CrIV-oxo
species, which polymerize ethylene at 25 °C (middle in Fig.1). We attributed the higher
reactivity to the CrIV-oxo sites being 10 times more active than CrII species [2].
b) Cyclohexene has is known to reduce the CrVI species [3]; we thus monitored the reduction
at 25 °C revealing the formation of two different type of Cr sites in interaction with aldehydes
and carboxylate species, polymerizing ethylene at 25 °C (right in Fig.1).
Figure 1: Reduction of the chromate species on the CrVI/SiO2 Phillips catalyst by means of: CO (left), CH4
(middle) and C6H10 (right).Middle and right reductions lead to the formation of dual site type of catalysts.
Keywords: Phillips catalyst, pre-reducing agents, ethylene polymerization
[1]M.P. McDaniel, Adv. Catal. 53 (2010) 123-606.
[2]E. Groppo et al., Chem. Eur. J. 17 (2011) 11110 – 11114
[3]W. Rohde, US. Patent 6147171 (2000).
80
CAT-15:Surface Reduction of TiO2 with Hydrosilanes:Conversion of Ethylene to HDPE
Without Alkylating Agent
C. Barzan1*, E.A. Quadrelli2, A. Zecchina1, S. Bordiga1 and E. Groppo1
2 - Universitè Claude Bernard Lyon 1, 43 B. du 11 Nov 1918, 69616 Villeurbanne, F
Since decades the electronic properties of reduced titanium dioxides (TiO2) are at the core of intense
interests in the fields of photocatalysis [1], solar energy production (coupled with organic dyes) [2] and
fuel cells. From a chemical point of view, reduced TiO2 is attractive because of the presence at the surface
of many defects potentially able to perform catalytic reactions. One of the possibilities is ethylene
polymerization and oligomerization, in analogy with Ti4-n reduced species present in Ziegler-Natta (ZN)
heterogeneous catalysts and in aryloxy- and alkoxy-Ti2+ complexes, respectively [3, 4].
In analogy to our work on defective thermally H2-reduced TiO2 performing ethylene polymerization, [6]
we explored the reduction of TiO2 materials with SiH4 at room temperature. By carefully analyzing the
time-resolved transmission FT-IR and Diffuse Reflectance UV-Vis spectra collected during the reduction,
we monitored the formation of hydrides (Ti-Hx) on the surface of nanoanatase, nanorutile and P-25
samples. Moreover, all the SiH4 reduced samples appear pale light blue in color due to the appearance of a
broad absorption through the whole UV-Vis – IR region that has been ascribed to the phenomenon called
Drude absorption. When ethylene is brought into contact with the SiH4 reduced TiO2 samples, the Ti-Hx
and the Drude absorption disappear while polymerization occurs leading to an highly crystalline HDPE.
High Resolution TEM evidenced the formation of a nanocomposite constituted by TiO2 and spot-like PE
on the surface of the particles. A summary of the reaction is shown in a simplistic way in Scheme1. The
ethylene polymerization mechanism cannot be the same happening on Ziegler-Natta catalysts, since here
no alkylating agent is required to perform ethylene polymerization. In this sense SiH4 reduced TiO2
materials show Ti active species more similar to the Cr sites in Phillips catalyst.
Scheme 1: Schematic representation of TiO2 reduction happening at RT with SiH4, leading to surface
reduced particles displaying Ti4-n reduced sites performing C2H4 polymerization without alkylating agents.
Keywords: Reduced TiO2, Hydrosilanes, Ethylene Polymerization, Nanocomposite
[1]
[2]
[3]
[4]
[5]
X.B. Chen, L. Liu, P.Y. Yu, and S.S. Mao, Science 331 (2011) 746-750.
G.M. Wang, et al., Nano Letters 11 (2011) 3026-3033.
Z.B. Ye et al., J. Pol. Sci. Pol. Phys. 41 (2003) 2433-2443.
J.A. Suttil et al., Dalton Transactions 41 (2012) 6625-6633.
C. Barzan, E. Groppo, S. Bordiga, and A. Zecchina, Acs Catal 4 (2014) 986-989.
81
CAT-16:1,2,3-Triazole Fluorescent Bisphosphonates as Osteoporosis Probes Drugs
Andrea Chiminazzo,1,* Boris A. Kashemirov,2 Charles E. McKenna,2Alessandro Scarso1
1 - Università Ca‟ Foscari di Venezia, Dipartimento di Scienze Molecolari e
Nanosistemi,Venezia, Dorsoduro 2137, 30123, Italy.
2 - University of Southern California, Department of Chemistry, Los Angeles, California
90089-0744, United States.
Thanks to their structural similarity with pyrophosphate, bisphosphonates (BPs) ensure specific
bone targeting and are widely employed as drugs for the treatment of bone disorders, in
particular osteoporosis whose costs, every year, were estimated in €37 billion treating
approximately 27.5 million affected people in Europe.[1] Recent studies have demonstrated that
zoledronic acid, one of the most potent drugs under use, characterized by the presence of a 1,3diazole bisphosphonate strucutre, is among the most efficient inhibitor of specific enzymes [2]
leading to osteoclast inactivation and apoptosis. In the present contribution we present the
syntheses of  and azido-BP “Click reaction reagents” in order to obtain a new potentially
highly efficient class of 1,2,3-triazole BPs. The synthesis of the -azido BP proceeded readily
via Pd(II)-catalyzed addition of azidotrimethylsilane [3] to vinylidenebisphosphonate
tetraethylesters (VBP), providing a quantitative yield of the desired compound, using an
improved procedure. -Azido BP can be obtained by Cu(II)-assisted diazo-transfer reaction to a
amino-BP using imidazole-1-sulfonyl azide hydrochloride as a safe diazo-transfer reagent
compared to the commonly employed triflyl azide.[4] These efficient syntheses allowed the
preparation of the azido-BPs in multigram scale that were tested in click chemistry reactions
(Cu(I)-catalyzed azide-alkyne cycloadditions), giving 1,4-di-substituted 1,2,3-triazoles BP
products with high regioselectivity. Reaction with several terminal alkynes, including a triplebond functionalized diketopyrrolopyrrole (DPP) fluorescent dye, gave a new class fluorescent
BP probes for bone imaging.
Keywords: bisphosphonate, azide, diazo-transfer, click chemistry, diketopyrrolopyrrole
* Corresponding author: Andrea Chiminazzo, [email protected]
References
[1] E. Hernlund, A. Svedbom, M. Ivergård, J. A. Kanis, Arch. Osteoporos. 8 (2013), 136
[2] Y. Zhang, R. Cao, J. Am. Chem. Soc. 131 (2009), 5153
[3] M. Ferrer-Casal, A. Barboza, H. Szajnman, J. Rodriguez, Synthesis 45 (2013), 2397
[4] H. Johansson, D. Pedersen, Eur. J. Org. Chem. (2012), 4267.
82
CAT-17:Experimental results and dynamic simulation of enriched air production by
water degassing for process intensification
C. Pirola 1,3, A. Comazzi 1,3*, F. Galli 1,3, C.L. Bianchi1,3, F. Manenti2, F. Rossi2
1 - Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi, 19 – 20133 Milano
(Italy).
2 - Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica “Giulio
Natta”, piazza Leonardo da Vinci 32, 20133 Milano, (Italy)
3 - Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, INSTM,
A new kind of chemical processes intensification can be obtained by the production of enriched
air (EA), i.e. an oxygen/nitrogen mixture with an amount of O2 in the range of 22-35 vol.%
from degassing of air saturated water by pressure or temperature action. The basic principle is
based on the different Henry‟s constant of oxygen and nitrogen in water [1]. EA can be directly
used in situ, in order to reduce the total flow of combustion air and the volume of the
combustion facilities. Alternatively, enriched air can be used for diving or sold for
industrial/medical uses [2]. Proper experimental tests were carried out in a laboratory batch
plant in order to optimize the two main operative parameters of this operation, i.e. T and P. The
obtained experimental data have been elaborated for the modeling of this technology in order to
validate the experimental runs and simulate the EA production process obtaining the optimal
conditions for the application in different chemical processes. Experimental tests were carried
out at 55 < T < 75 °C and 260 < P < 500 torr. The elaborated EA model is a non-linear
differential-algebraic equations system (DAE), based on two equation sets: the first relates to
the degasser while the second refers to the enriched air storage; thus specific numerical tools
must be employed in its resolution. Here, BzzMath library is employed for this purpose. In
Figure 1 a comparison between experimental data (points) and simulated data (continuous line)
is reported at 75°C and 260 torr. From the obtained
experimental data is possible to observe that the
best condition in term of %O2 and produced
volume of EA is at 260 torr and 75°C because at
this couple of T and P all the oxygen dissolved in
water is totally degassed. In addition, the dynamic
model elaborated shows a good agreement with the
achieved experimental data.
Figure 1: Exp and model results
Keywords: Enriched Air, Process Intensification, Dynamic Simulation
* Corresponding author: Alberto Comazzi, [email protected]
References
[1] W.M. Haynes, Handbook of Chem and Phys, 93rd ed., CRC, Taylor and Francis, LLC, 2013
[2] F. Manenti, C. Pirola, Chem Eng and Proces: Process Intens 79 (2014) 40
83
CAT-18:Co and Co/Ru based catalysts synthesized by FSP for the industrial Gas-toLiquid Fischer-Tropsch process
A. Comazzi 1,2*, F. Galli 1,2, C.L. Bianchi1,2, I. Rossetti1,2, F. Manenti3, C. Pirola 1,2, A. Di
Michele4
1 - Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi, 19, 20133 Milano
2 - Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, INSTM,
3 - Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica “Giulio
Natta”, piazza Leonardo da Vinci 32, 20133 Milano
4- Università degli Studi di Perugia, Dipartimento di Fisica, via Pascoli 1, 06123 Perugia
The GTL - FT process converts syngas, a mixture of H2/CO with a molar ratio equal to 2, into
hydrocarbons [1]. A 10%wtCo and a 10%wtCo - 0.1%wtRu based catalysts supported on silica
were prepared by Flame Spray Pyrolysis (FSP), chatacterized by
BET, SEM, TEM, TPR, XRD and tested at different temperature
in a FT bench scale plant using a Packed Bed Reactor (PBR).
FSP allows to obtain metal oxides with high surface area and
high thermal stability thanks to the dispersion, vaporization and
pyrolysis of the precursors solution [2]. The solution is composed
of Co(CH3COO)2·4H2O (Fluka), Si(OC2H5)4 (Fluka) dissolved in
a 1/1 (vol/vol) mixture of CH3CH2COOH (Fluka)/p-xylene
(Sigma Aldrich). The synthesis of the bimetallic catalyst is
accomplished by FSP followed by the addition of Ru by
impregnation using Ru3(CO)12 (Sigma Aldrich) as a precursor.
The TPR profiles (Figure 1) of both samples show two different
peaks at T= 320-360°C (Co3O4CoO) and T= 700-800°C
Figure 1: TPR profiles
(CoOCo) [1]. Figure 1 also highlights that the insertion of
Ru decreases both peaks temperatures by ca. 20°C. The samples were tested at T= 225-260°C,
P= 2.0 MPa, H2/CO= 2 (mol/mol) with sl/h/gcat= 3.0. The results summarized in Table 1 show
that Co-Ru is more active in therms
Selectivity (%)
CO
T
of CO conversion and C2+yeld if
Conv.
C2+ CO CH <C >C
(°C)
(%)
compared with the monometallic
2
4
7
7
245
23.4
20.4
1
12
10
77
one. The non-promoted catalyst
Co
255
60.7
54.0
1
10
10
79
shows higher selectivity to >C7 with
260
98.8
82.0
6
11
10
73
respect to the Ru-doped catalyst.
225
55.8
50.2
1
9
18
72
Finally, the selectivity toward the
Co230
73.2
65.1
2
9
17
72
Ru
reaction products is not largely
245
94.5
77.5
6
12
14
68
influenced in the range of
temperature tested.
Table 1: Catalytic results of Co and Co-Ru catalysts
Keywords: Fischer-Tropsch, Flame Spray Pyrolysis, Co-based catalysts
* Corresponding author: Alberto Comazzi, [email protected]
References
[1] C. Pirola, C.L. Bianchi, A. Di Michele, S. Vitali, V. Ragaini, Cat. Comm. 10 (2009) 823
[2] H. Jang, C. Seong, Y. Suh, H. Kim, C. Lee C, Sci. and Tech. 38 (2004) 1027
84
CAT-19:One Pot Synthesis Of Linear Alkylbenzenes From Styrene, Ethylene And
Hydrogen
Nunzia Galdi *, David Hermann Lamparelli, Leone Oliva.
Dipartimento di Chimica e Biologia, Università di Salerno, 84084 Fisciano (SA)
The alkylbenzenes are widely used as intermediates for the production of detergents, their
sulfonation giving rise to anionic surfactants of relevant commercial interest. Among the
alkylbenzene sulfonates particular attention is paid to the linear ones due to the faster and more
complete biodegradation that makes them preferable as eco-friendly products.1 The synthesis of
the alkylbenzenes is generally obtained through benzene alkylation by employing 1-alkenes as
reactants, which in turn can be the product of the ethylene oligomerization.
In this communication we report the investigation on the possible one-pot synthesis of LAB‟s
starting from largely available commodities such as ethylene, styrene and hydrogen, in mild
experimental conditions. The tool identified to attain this goal is the polyinsertion catalysis of
the olefins, which, in its homogeneous variation, offers a large armory of catalysts having
different behaviors towards the title reagents both with respect to the relative reactivity of
styrene, ethylene and hydrogen and with regard to the regiochemistry of the styrene insertion.
The latter aspect is crucial in order to avoid the short branches formation that is detrimental for
the biodegradability of the detergents.
Actually the judicious choice of a zirconium complex as catalyst component, also in the light of
previous studies on the regiochemistry of the styrene insertion, 2 allows the selective synthesis of
linear alkylbenzenes with 12-14 carbons as average length of the aliphatic chain. Such LAB‟s
represent the ideal precursors for the production of anionic surfactants. 3
Keywords: linear alkylbenzene, polyinsertion catalysis
References
[1] J. L. G. de Almeida, M. Dufaux, Y. Ben Taarit, C. Naccache, JAOCS 71 (1994) 675
[2] A. Correa, N. Galdi, L. Izzo, L. Cavallo, L. Oliva, Organometallics 27, (2008) 1028
[3] E.S. Sadlowski, C. Thomas, P. De Nies, N. E. Aksoy, US Patent 8729007 (2014) Procter &
Gamble Co
85
CAT-20:Photocatalytic removal of Patent Blue V dye on Au/TiO 2 catalysts
Vincenzo Vaiano1, Giuseppina Iervolino1* , Diana Sannino1, Paolo Ciambelli1, Julie .J.
Murcia2, Maria C. Hidalgo3 and Josè Navío3
1- Department of Industrial Engineering, University of Salerno, via Giovanni Paolo II, 132,
84084 Fisciano (SA) Italy
2- Universidad Pedagógica y Tecnológica de Colombia, Boyacá – Colombia
3- Instituto de Ciencia de Materiales de Sevilla (ICMS), Consejo Superior de Investigaciones
Científicas (CSIC), Universidad de Sevilla, Américo Vespucio 49, 41092 Sevilla – Spain.
In this work it was studied the efficiency of a photocatalytic process for the removal of Patent
Blue V, difficult to remove with conventional treatments such as adsorption or coagulation. The
photocatalytic process is very interesting for the removal of dyes as it does not require
expensive oxidants and can be carried out at mild temperatures and pressures. The
photocatalytic degradation of Patent Blue V has been investigated in literature by using TiO 2
(Degussa P25) in presence of different electron acceptors such as H 2O2 or KBrO3 [1]. In this
work it was tested the efficiency of Au/TiO2 photocatalysts prepared by photodeposition
method. The Au content was 0.3 wt%. The presence of noble metals suppress to some extent
the charge carriers recombination enhancing the photocatalytic activity [2]. The influence of
some parameters, such as photodeposition time (15 or 120 min) and the intensity of light source
using in photodeposition method (0.14 or 140 W/m2) was evaluated. Photocatalytic experiments
were carried out with a Pyrex cylindrical reactor irradiated by UV-LEDs with wavelength
emission in the range 375–380 nm. The catalyst dosage was 3 g/L and the initial concentration
of dye was 7 mg/L. The presence of Au on the titania surface enhanced the photocatalytic
removal of the target dye. In fact, after 3 hours of irradiation time, on the catalyst prepared with
light intensity equal to 140 W/m2 and 15 min of photodeposition time, a decolourization and a
TOC removal of 70 and 57% respectively, has been achieved, higher than that obtained on TiO 2
alone (decolourization and TOC removal of about 25%).
Keywords: photocatalysis, dye, patent blu V, Au/TiO2
* Corresponding author: Giuseppina Iervolino, e-mail contact : [email protected]
References
[1] M. Saquib, M. Abu Tariq, M. Faisal, M. Muneer, Desalination 219 (2008) 301–311.
J. Xhie, K. Sattler, M. Ge, N. Venkateswaran, Phys. Rev. B 47 (1993) 15835
[2] A. L Linsebigler, G. Lu, and J. T. Yates, Chemical Reviews, 95(3) (1995) 735-758.
86
CAT-21:Role of acid sites in porous silica catalysts for selective production of biodiesel
additives
K. Barbera, P. Lanzafame*, S. Perathoner, G. Centi
University of Messina, Department of Electronic Engineering, Chemistry and Industrial
Engineering and CASPE-INSTM, Viale F. Stagno d‟Alcontres, 98166 Messina, Italy
The activity of acid catalysts in the conversion reaction of biomass derivatives to employable
diesel-range products has been widely explored, evidencing how the nature and the strength of
active sites influence the catalytic performances [1-2]. In case of 5-hydroxymethyl-2-furfural
(HMF), the main products in the acid-catalyzed conversion of ligno-cellulosic biowastes, the
selectivity in the etherification with ethanol to biodiesel components, 5-(ethoxymethyl)furfan2-carbaldehyde (EMF) and ethyl-4-oxopentanoate (EOP), is influenced by the different nature
of Lewis and/or Brønsted acid sites (Fig. 1) [3].
Fig. 1. Etherification of 5-(hydroxymethyl)furfural (HMF) with ethanol
However, a low selectivity due to competition reaction, such as acetalization and furan ring
opening reaction, is often observed. For this reason, the aim of this work is to investigate the
role played by acid sites in influencing the reactivity and selectivity in HMF etherification. This
aspect results of note not only for the applicative interest of the products as biodiesel additives
but also for its fundamental character.
Two classes of silica-based catalysts, with different textural properties, such as mesoporous
SBA-15 and microporous Silicalite-1 were selected and the amount, the strength and the nature
of the reactive sites were modified by introduction of ZrO 2 and subsequent sulphation reaction
for mesoporous SBA-15 and by post synthesis treatments (ionic-exchange, thermal treatment
and silylation) for microporous Silicalite-1.
Keywords: acid sites, HMF etherification, biodiesel additives
References
[1] Y. M. Sania, W. M. A. W. Dauda, A. R. A. Aziza, Appl. Catal. A: Gen. 470 (2014) 140
[2] K. Barbera, P. Lanzafame, A. Pistone, S. Millesi, G. Malandrino, A. Gulino, S. Perathoner,
G. Centi, J. Catal. 175 (2015) 19
[3] P. Lanzafame, D. M. Temi, S. Perathoner, G. Centi, A. Macario, A. Aloise, G. Giordano,
Catal. Today 175 (2011) 435
87
CAT-22:Selective oxidations of biomass resources on Au/ZrO2 catalysts doped by
sulphates
Federica Menegazzo1*, Alberto Olivo1, Michela Signoretto1, Francesco Pinna1, Maela
Manzoli2
1 - Department of Molecular Sciences and Nanosystems, Ca‟ Foscari University Venice and
INSTM-RU Ve, Dorsoduro 2137, 30123 Venezia (Italy)
2 - Department of Chemistry & NIS Interdepartmental Centre, University of Turin, Via P.
Giuria 7, 10125 Turin (Italy)
The nonedible nature of lignocellulose, which implies no competition with food, makes this an
important raw material for biorefineries in the future. The transformation of selected platform
molecules is the most appropriate approach for identifying molecules that can replace those
coming from petrolchemistry or for the generation of new molecules. The present work deals
with liquid phase selective oxidations of 5-hydroxymethylfurfural (HMF) to 2,5
dimethylfuroate (FDMC, a monomer for the replacement of terephtalic acid in plastics) and of
glucose to gluconic acid. Gold nanoparticles supported on zirconia [1] are efficient catalytic
systems for these reactions even without the use of a base, making the process green and
economically advantageous. The role of the sulphation degree of zirconia on the nature and
dispersion of supported gold species and consequently on the catalytic properties is here
investigated. As for HMF oxidative esterification, all catalysts reached complete conversion
while selectivity displayed a bell-shaped trend. In particular, the maximum selectivity is
reached when the catalyst are doped with 2 wt% sulphates. Also for glucose oxidation, the
catalytic performances evidenced the positive effect of sulphate doping. The best results are
obtained with the sample doped with a low amount of sulphates. It can be assumed that there is
a range of sulphates concentration in which they have a positive effect on the activity. In order
to elucidate the reasons for such effect, the samples have been extensively characterized by
XRD, DRUV-Vis and FTIR spectroscopies, N2 physisorption, CO pulse chemisorption
measurements and HRTEM. It has been found that the reactivity is related not only to the Au
active phase, in terms of loading and dispersion, but it is also closely tied to its distribution on
the support. The amount of sulphate groups present on bare zirconia plays a role on the gold
dispersion and consequently on the catalytic properties. An effect on the final shape of gold
nanoparticles has been put in evidence: irregular plate-like gold nanoparticles can affect the
selectivity to FDMC and conversion to gluconic acid. Such SO 4= promotion is carried on in a
well defined concentration range. Structure-properties relationships have been determined and a
model has been proposed.
Keywords: gold catalysts, oxidation, HMF, glucose
* Corresponding author: Federica Menegazzo, e-mail contact: [email protected]
Reference
[1] F. Menegazzo, T. Fantinel, M. Signoretto, F. Pinna, M. Manzoli, J. Catal. 319 (2014) 61
88
CAT-23:Selective and Efficient Reduction of Nitrobenzene to Aniline catalyzed by AuNPs
Embedded in a Nanoporous Crystalline Polymeric Support
Annarita Noschese1*, Antonio Buonerba1, Carmine Capacchione1, Stefano Milione1,
Alfonso Grassi1
1 - Dipartimento di Chimica e Biologia, Università degli Studi di Salerno, Via Giovanni Paolo
II - 84084 Fisciano (SA), Italy, and CIRCC-Bari, Italy
Supported Gold Nanoparticles (AuNPs) efficiently catalyze both oxidation and reduction
reactions. E.g. aerobic oxidation of alcohols and cross coupling reactions of alcohols leading to
esters, amide, imine have been widely and successfully explored [1]. On the other side the
reduction of nitroarenes to anilines using NaBH4, H2, silanes, formic acid, CO/H2O is a
benchmark reaction for testing their catalytic performances in reduction reactions [2].
During reaserch efforts many supports have been exploited (carbon based supports, polymers,
inorganic oxides) but their role is still under discussion. A semicrystalline porous polymeric
support, consisting of syndiotactic polystyrene-co-cis-1,4-polybutadiene [3] has been
successfully tested in our group and the AuNPS embedded in this polymer matrix (AuNPssPSB) were investigated in the reduction of nitrobenzene to aniline . The polymorphic behaviour
of the host polymer matrix has been studied to optimize the catalyst performances. The
nanoporous crystalline forms of the sPSB matrix, namely  and , allowed a total conversion of
nitrobenzene in 40 min at room temperature, with 100% selectivity in aniline. On the contrary
the not permeable  crystalline form gave a less reactive and selective catalyst; actually
azobenzene and azoxybenzene were detected as intermediates compounds providing
information on the cascade of the reduction reactions and the global reaction mechanism.
Among the catalysts to date reported in the literature, the AuNPs-sPSB catalyst showed the
highest activity (TOF=6000 h-1). The catalyst is very stable under the reaction conditions and
reusable for at least three times without loss of catalytic activity.
Keywords: Gold Nanoparticles, Polymeric Matrix, Reduction.
References
[1] A. Corma, H. Garcia, Chem. Soc. Rev. 37 (2008) 2096
[2] S. Fountoulaki, V. Daikopoulou, P. L. Gkizis, I. Tamiolakis, G.S. Armatas, I. N. Lykakis,
ACS Catal. 4 (2014) 3504; X. Liu, S. Ye, H.-Q. Li, Y.-M. Liu, Y. Cao, K.-N. Fan, Catal. Sci.
Technol. 3 (2013) 3200; L. He, L.-C. Wang, H. Sun, J. Ni, Y. Cao, H.-Y. He, K.-N. Fan,
Angew. Chem. Int. Ed. 48 (2009) 9538.
[3] A. Buonerba, C. Cuomo, S. Ortega Sánchez, P. Canton, A. Grassi, Chem. Eur. J. 18 (2012)
709; A. Buonerba, A. Noschese, A. Grassi, Chem. Eur. J. 20 (2014) 5478.
89
CAT-24:Study of photoreactor design for sustainable carbon dioxide photoreduction
Alberto Olivo1*, Elena Ghedini1, Michela Signoretto1, Francesco Pinna1, Valentina
Trevisan 1, Giuseppe Cruciani 2
1 - Dept. of Molecular Sciences and Nanosystems, Ca' Foscari University Venice and
Consortium INSTM, RU of Venice, Dorsoduro 2137, 30123 Venice, Italy
2 - Dept. of Physics and Earth Sciences, Ferrara University, via G. Saragat 1, 44121 Ferrara,
Italy
One of the most important challenges of the 21 st century is the continuous increase in carbon
dioxide emissions in atmosphere. CO2 is the most abundant greenhouse and derives from fossil
fuels utilization for human activities. Their use is definitely not environmentally sustainable and
research is addressed to innovative technologies for fuels production. Therefore fighting CO2
emissions and finding alternative and sustainable energy sources are strictly connected one to
another. Photocatalysis is a key technology to abate the CO 2 emissions and to transform them
into fuels [1]. Among them, the most important product is methane, that can be obtained from
carbon dioxide photoreduction using water as an environmentally friendly reducing agent.
Titania has proven to be a good photocatalyst for this reaction, but a large scale application is
still long to come. Generally, this reaction is performed under pressure and in liquid alkali
media in order to overcome poor CO2 solubility, though the addition of a base makes the
process less sustainable [2]. In literature only few examples of gaseous CO 2 photoreduction are
reported and the reaction is carried out by using hard conditions in terms of temperature (up to
100°C), pressure and irradiance (up to 500 W• m-2)[3].
The aim of this work is to improve CO2 photoreduction efficiency in mild conditions: room
temperature atmospheric pressure and, most importantly, low irradiance. Several TiO 2
photocatalysts have been prepared using the sol-gel technique considering synthetic parameters
such the presence of retarding agents and calcination temperature. Two different reactors have
been investigated: a fixed bed reactor and a thin film reactor, both characterized by the same
dimensions. Catalysts physicochemical properties have been correlated to photocatalytic
activity.
Keywords: CO2 reduction, photocatalysis, titania, mild conditions
References
[1] G. Centi and S. Perathoner, Catal.Today 148 (2009) 191.
[2] S. Das, W. M. A. Wan Daud, Renew. Sust. Energ. Rev. 39 (2014) 765.
[3] M. Tahir, N.S. Amin, Appl. Catal. B 162 (2015) 98
90
CAT-25:B-site Pd and Ni promoted La0.6Sr0.4Co0.2Fe0.8O3-δ perovskites as IT-SOFCs
cathodes
F. Puleo1 *, S. Guo1,2, V. La Parola1, C. Lo Cascio1, N. Yigit3, G. Rupprechter3, L.F.
Liotta1
1 - Istituto per lo Studio di Materiali Nanostrutturati CNR-ISMN, Via Ugo La Malfa 153, 90146
Palermo, Italy.
2 - Northwestern Polytechnical University, Xi‟an 710072 PR China.
3 - Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/BC,
1060 Vienna, Austria
Thanks to their mixed ionic/electronic conductivity and high catalytic activity for oxygen
exchange reaction, La1−xSrxCo1−yFeyO3-δ (LSCF) perovskites have received much attention as
cathode materials for intermediate solid oxide fuel cells (IT-SOFCs) operating at relatively lowtemperature, 600-800 °C. Lowering the operating temperature, however, decreases the electrode
kinetics, in particular the oxygen reduction at the cathode.
It is widely accepted that the rate-limiting step of O2 reduction process is the solid state
diffusion of oxygen anions through the vacancies of the cathode lattice. LSCF oxides with
metal substitution in B-site prepared by different methods, such as solid-state reaction or by
impregnation of the perovskite with the metal dopant precursor, have been extensively
investigated as new cathodes with enhanced oxygen reduction activity [1].The promotion of
redox properties of La0.6Sr0.4Co0.8Fe0.2O3-δ and of La0.6Sr0.4Co0.2Fe0.8O3-δ by incorporation of
Pd4+ into the B-site of the perovskite lattice, through one pot citrate synthesis, has been recently
demonstrated by some of us [2]. The present work aims to get more insight into the B-site metal
promotion by investigating the effect of two metals (Pd and Ni) and by using citrate-EDTA
method that provides a good control of the microstructural properties. Two perovskites with
compositions La0.6Sr0.4Co1-xFex-0.03M0.03O3-δ (x=0.2/0.8; M=Pd/Ni) have been prepared and
compared with the un-promoted La0.6Sr0.4Co0.2Fe0.8O3-δ cathode material. Characterizations by
XRD, TPR, XPS, TGA, CO FT-IR, CO-TPD, EIS techniques have been carried out. Addition of
Pd and Ni to La0.6Sr0.4Co0.2Fe0.8O3-δ was found to be effective in improving the redox and
electrochemical properties.
Keywords: LSCF, IT-SOFC, cathode, EIS, perovskite
Acknowledgements
S. Guo thanks COST Action CM 1104 (COST-STSM-ECOST-STSM-CM1104-270415056579) and China Scholarship Council for financial support. C. Lo Cascio thanks the Regione
Siciliana, Progetto N. 20 (ID 11) ”Nanomateriali e Nanotecnologie per lo Sviluppo Sostenibile
ed il Patrimonio Culturale”.
References
[1] S. Guo, H. Wu, F. Puleo, L.F. Liotta, Catalysts 5 (2015) 366
[2] F. Puleo, L. F. Liotta, V. La Parola, D. Banerjee, A. Martorana, A. Longo, Phys. Chem.
Chem. Phys. 16 (2014) 22677
91
CAT-26:Hard-Templated NiO-CeO2 mixed oxides as catalysts for CO2 methanation
E. Rombi*, M. G. Cutrufello, L. Atzori, D. Meloni, R. Monaci, I. Ferino
Dipartimento di Scienze Chimiche e Geologiche, Università di Cagliari, Complesso
Universitario di Monserrato, S.S. 554 bivio Sestu, 09042 Monserrato (CA), Italy
Methanation reaction has been mainly investigated using Ni-based catalysts, due to their low
cost, high activity and high methane selectivity. The effect of different promoters, supports, and
preparation methods on the catalytic activity and stability of Ni-based catalysts has been studied
[1]. Among the preparation procedures, the hard-template method (HT) has attracted increasing
interest for the synthesis of ordered mesoporous non-siliceous metal oxides, using a
mesostructured silica as template [2]. In this work, two different mesoporous NiO-CeO2
systems (Ni = 4 ÷ 35 wt%) were synthesized (i) by the HT procedure using SBA-15 as the
template or (ii) by impregnating NiO on a hard-templated CeO2. Two NiO-Al2O3 catalysts (Ni
= 11 and 25 wt%) were also prepared for comparison. The obtained samples were named
NiCe(x)_HT, NiCe(x)_IM, and NiAl(x)_IM, respectively, where x represents the actual wt% of
Ni). They were characterized as to their composition, structure, texture, and redox features. CO2
methanation was investigated at atmospheric pressure and 300 °C, after reduction of the
catalysts with H2 at 400 °C for 1 h. All samples showed type IV N2 adsorption/desorption
isotherms, typical of mesoporous solids. Surface areas were in the range 80-180 m2 g-1. The
pore size distribution curves of the hard-templated catalysts exhibited a peak at ~ 3.0 nm
(corresponding to the wall thickness of SBA-15), indicating that the negative replica of the
template was, at least partially, obtained. XRD patterns of the fresh samples showed the typical
reflections of crystalline NiO, with particles size in the range 10-23 nm, depending on the
preparation method, the Ni content, and the type of support. H 2-TPR results indicated that NiO
is more easily reduced in both the NiCe(x) systems in comparison with NiAl(x)_IM catalysts.
NiCe(x)_HT and NiCe(x)_IM samples showed a high methanation activity, with CO 2
conversions (XCO2) ranging from 30 to 65 mol% and showing a maximum at Ni amounts of 24
wt% (XCO2 = 65 mol%) and 14 wt% (XCO2 = 60 mol%) for the HT and IM series, respectively.
XCO2 values ≤ 20 mol% were found for the NiAl(x)_IM catalysts. XRD analyses on the
NiCe(24)_HT, NiCe(24)_IM, and NiAl(25)_IM after the H 2 pretreatment pointed out to the
formation of Ni0 nanocrystals of 15, 29, and 46 nm, respectively. The obtained results
highlighted that (i) the HT method allows to obtain a good dispersion of higher amounts of NiO
compared to the conventional impregnation procedure, and (ii) CeO 2 performs better than Al2O3
in preventing the agglomeration of Ni0 particles resulting from NiO reduction.
Keywords: CO2 methanation, hard-template, Ni-Ce oxides
* Corresponding author: e-mail [email protected]
References
[1] Q. Pan, J. Peng, T. Sun, S. Wang, S. Wang, Catal. Commun. 45 (2014) 74
[2] D. Gu, F. Schüth., Chem. Soc. Rev. 43 (2014) 313
92
CAT-27:An innovative method for the estimation of AN storage over commercial Cuzeolite catalysts for automotive applications
Maria Pia Ruggeri, Isabella Nova, Enrico Tronconi*
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di
Milano, via La Masa 34, 20156 Milano (Italy)
NH3-SCR represents the leading technology for NOx abatement from Diesel exhaust. However,
the limited volume available on board and a continuous demand for more efficient DeNOx
performance in the low temperature range urges for more technological improvements. As an
example, Enhanced-SCR reaction is a cutting edge technology consisting in the addition of an
aqueous solution of ammonium nitrate (AN) together with gaseous NH 3 (or NH3 from Urea
decomposition) upstream the SCR converter, resulting in the very fast reaction: 2 NH 3 + 2 NO
+ NH4NO3 → 3N2 + 5 H2O. In such a way, it is possible to boost the SCR DeNOx activity,
approaching the optimal Fast-SCR conditions, without the need of any DOC upstream. The
Enhanced-SCR reaction has already shown its promising results over both V 2O5-WO3/TiO2 and
Fe-ZSM-5 commercial catalysts [1, 2]. Nevertheless, in order to develop and optimize the
performance of the entire aftertreatment system, it becomes crucial to obtain an estimate of AN
storage on the catalyst under real application conditions. In this work, we develop a very simple
method to estimate AN storage on a commercial Cu-zeolite catalyst. The method was initially
developed on the catalyst in the form of powder loaded in a quartz microreactor (80 mg). He
was used as balance gas; gas phase concentrations were monitored by a UV analyzer coupled
with a mass spectrometer in order to evaluate selectivity to N 2 and N2O. AN was generated in
situ, by cofeeding NH3 and NO2 at temperatures as low as 180-200°C. Then, the amount of AN
deposited onto the catalyst was evaluated during reaction with NO, by calculating integral mass
balances including NO consumption, and NO2, N2 production. The method was then validated
on the catalyst used in the form of core monolith sample (≈ 6 cm3), under different flow
conditions and by feeding AN directly from a 0.1M aqueous solution, using a peristaltic pump.
A good match between the estimates and the amount of AN fed to the catalyst was obtained.
Thus, the method developed in this study is both effective and of practical interest.
Keywords: E-SCR, ammonium nitrate, Fast SCR, NOx abatement, Cu zeolite
References
[1] P. Forzatti, I. Nova, E. Tronconi, SAE Int. J. Fuels Lubr. 3 (2010) 654
[2] P. Forzatti, I. Nova, E. Tronconi, A. Kustov, J.R. Thøgersen, Catal. Today 184 (2012)
153
93
CAT-28:Experimental and modeling study of hydrocarbon inhibition effects on NH 3-SCR
over metal promoted zeolite catalysts
Tommaso Selleri 1, Isabella Nova 1, Enrico Tronconi 1*, M. Weibel 2, V. Schmeißer 2
1 - Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di
Milano,
Via La Masa 34, I-20156, Milano (Italy)
2 - Daimler AG, 019-G206 RD/RPE, 70546 Stuttgart (Germany)
Despite being the leading technology in the NOx abatement from lean burn engines, NH 3
selective catalytic reduction (SCR) still presents some fundamental issues that need to be
elucidated, such as the low-T and cold start behavior. In these conditions the catalytic devices
constituting the after-treatment train are not operative, leading to a significant hydrocarbon
(HC) slip that impacts negatively on the SCR catalyst [1]. The aim of this contribution is to
clarify the main phenomena involved in the HC poisoning of different catalysts (Fe- and Cuzeolites) and develop a reliable numerical simulation tool of the deactivation process. To this
purpose, a systematic set of experimental data has been collected. This includes the study of
light (C3H6) and heavy (C10H22) HC adsorption, also in presence of O2 and H2O. Moreover, the
possible relevance of competitive adsorption between NH3 and HC has been investigated [2]. In
addition, light and heavy HC oxidation tests have been performed to analyze the T activated
deactivation effect reported in literature [1]. Finally, the impact of different HCs on SCR
reactions performances both in steady state and TRM tests has been studied. Based on the
experimental evidence collected, the deactivation process is modeled according to a dual site
approach, including: i) a redox site (S1), where NO is oxidatively activated and HC poisoning
occurs due to partial oxidation, intermediate adsorption and coke formation; ii) an acid site (S2),
responsible for ammonia adsorption and HC adsorption. Two lumped HC molecules are
considered as representative of light HC and heavy HCs. Light lumped HC compounds are
known to adsorb to a negligible extent on acid sites. For this reason a spillover mechanism from
acid to redox metal sites, similar to the one proposed for NH 3 in [3], is introduced in the model.
Light HCs undergo an O2-activated step on the catalyst leading to the poisoning of redox metal
sites. In this way, experimental effects both on the ammonia storage and desorption dynamics
but also on the catalytic activity are described correctly. On the contrary, heavy molecules are
assumed to directly adsorb on S2 sites, competing with NH 3, as reported in [2]. Moreover HC
oxidation by NO2 is accounted for in the model, being crucial to accurately describe the
poisoning effect on NO2-related reactions, like the Fast SCR. The kinetic model has been kept
as simple as possible in order to avoid significant impact on computation time. Nevertheless, it
covers several different effects reported in literature, and has shown satisfactory results in
predicting the HC impact on NH3-SCR catalysts.
Keywords: HC poisoning, deactivation, zeolites, lumped kinetic model, NH 3-SCR
References
[1] J.Luo, H.Oh, C.Henry, W.Epling, Appl.Catal.B: Env., 123 (2012) 296.
[2] I.Malpartida, O.Marie, P.Bazin, M.Daturi, X.Jeandel, Appl.Catal.B: Env., 102 (2011) 190.
[3] I.Nova, C.Ciardelli, E.Tronconi, D.Chatterjee, B.Bandl-Konrad, AIChE J.,52 (2006) 3222.
94
CAT-29: Heterogeneous catalysis for the production of 5-hydroxymethyl-2-furfural and of
2,5-bis(hydroxymethyl)furan from fructose and inulin
Claudia Antonetti 1*, Domenico Licursi 1, Elisa Bertolucci 2, Sara Fulignati 1, Marco
Martinelli 1, Anna Maria Raspolli Galletti 1
1 – Department of Chemistry and Industrial Chemistry, University of Pisa, Via Moruzzi 13,
56124, Pisa, Italy.
2 – Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126, Pisa, Italy.
Today, the sustainable growth of the chemical and energy industries has become an
indispensable benchmark of our society and the current development of the industrial sector
based on fossil resources must be replaced by an alternative one, linked to renewable resources.
By 2030, 30 % of the chemicals and materials production in Europe will be bio-based.
Therefore, the catalytic conversion of renewables is a promising and important topic, in
particular for the synthesis of 5-hydroxymeththyl-2-furfural (HMF) and of 2,5bis(hydroxymethyl)furan (BHMF) which find several applications in many strategic fields [12]. However, their productions from biomasses in water show remarkable drawbacks due to the
fast rehydration of HMF to formic and levulinic acid together with the formation of humins
which can passivate the catalyst. Consequently, from the point of view of sustainability and of
an integrate approach based on the biorefinery concept, the conversion of fructose and inulin to
HMF has been studied in the respect of green chemistry principles, adopting only water as
reaction medium, employing very low amounts of the heterogeneous acid catalyst Amberlyst A
70 and performing the reactions both in autoclave and in the presence of microwave irradiation.
The optimization of the reaction conditions allows us to reach in only water yields to HMF
higher of 40 mol % at 180°C for 20 minutes in the MW reactor employing a fructose/Amberlyst
ratio of 80 (wt/wt). In the same reaction conditions it is possible to obtain analogous
performances starting from inulin, highlighting the efficiency of this heterogeneous catalyst
when employed in very low amount also towards a more complex matrix. The obtained aqueous
solutions containing HMF, after removing the acid catalyst have been directly hydrogenated to
BHMF using Pt/C as catalysts. The preliminary achieved results show complete conversion of
HMF to BHMF, thus reaching yields to BHMF higher than 40 mol % respect to the starting
carbohydrate substrate.
Keywords: fructose, inulin, 5-hydroxymeththyl-2-furfural, 2,5-bis(hydroxymethyl)furan
* Corresponding author: Claudia Antonetti, [email protected]
References
[1] A. Mukherjee, M.J. Dumont, V. Raghavan, Biomass and Bioenergy 72 (2015) 143
[2] M. Chatterjee, T. Ishizaka, H. Kawanami, Green Chem. 16 (2014) 4734
95
INORG-01:Industrially-scalable encapsulation of flexible, microfluidic and polymeric dyesensitized solar cells
Federico Bella *, Andrea Lamberti, Stefano Bianco, Elena Tresso, Claudio Gerbaldi,
Fabrizio Pirri
Politecnico di Torino, Department of Applied Science and Technology (DISAT), Corso Duca
Degli degli Abruzzi 24 – 10129 – Torino (Italy)
One of the possible applications of dye-sensitized solar cells (DSSCs) is the biasing of lowpower portable devices. However some critical issues still have to be faced in view of obtaining
flexible cells, readily adaptable to complex shapes. Until today the best performing DSSCs are
based on a rigid housing with glass/FTO electrodes and the use of a liquid electrolyte is critical
for the possible durability of the device. Therefore, suitable flexible electrodes and polymeric
electrolytes are needed.
During recent years we deepened a promising approach for the fabrication of quasi-solid
DSSCs with excellent long-term durability. We thoroughly studied and characterized the
integration of self standing polymeric membranes prepared by free radical photopolymerization,
investigating different polymeric formulations. Very recently, this electrolytic system was
integrated with an innovative design for DSSC photoanode, based on the use of semitransparent
metallic meshes as a support for the sensitized nanostructured semiconductor [1]. For
photoanode fabrication, both the use of TiO2 nanotubes directly grown on bendable Ti mesh by
anodic oxidation and the deposition of mesoporous layers of TiO 2 nanoparticles were
investigated with excellent results. The main advantage of this solution is the possibility to
perform the high temperature sintering process (which is mandatory for a well performing
semiconductor layer with good electron transport properties) before the integration on the final
polymeric housing of the cell.
In this work, two flexible electrodes (a titanium mesh supporting N719-sensitized TiO2
nanotubes by anodic oxidation and a Pt-coated mesh) are embedded in flexible PDMS
substrates obtained by partial crosslink reaction before bonding. PDMS is almost totally
transparent to VIS radiation down to 220 nm, thus it represents a valuable substrate for flexible
DSSCs. Moreover, the two PDMS substrates can be sealed by means of a industrially-scalable
UV-curable siloxane methacrylate, thus avoiding the use of thermoplastic films that would
require pressure and high temperatures. Furthermore, PDMS is well suited for the fabrication of
microfluidic devices [2], so it is possible to create holes and channels for the introduction of
liquid electrolytes in large devices or UV-curable monomers containing different redox couples.
The photovoltaic behavior of the resulting solid DSSCs is exhaustively investigated by
electrical measurements and impedance spectroscopy. Preliminary results are definitely
encouraging since efficiencies as high as 4% are obtained in bended configuration.
Keywords: dye-sensitized solar cells, polymer electrolyte, microfluidic, nanostructures
[1] F. Bella, A. Lamberti, A. Sacco, S. Bianco, A. Chiodoni, R. Bongiovanni, J. Membr. Sci.
470 (2014) 125
[2] A. Lamberti, A. Virga, A. Angelici, A. Ricci, E. Descrovi, M. Cocuzza, F. Giorgis, RSC
Adv. 5 (2015) 4404
96
INORG-02:Graphene Coated FeCo Nanoparticles for Supercapacitors
Eleonora Ponticorvo*1, Maria Sarno1,2, Claudia Cirillo2, Carmela Scudieri1, Paolo
Ciambelli1,2
1 - Department of Industrial Engineering, University of Salerno, Italy
2 - NANO_MATES Research Centre, University of Salerno, Italy
Supercapacitors (SC) have attracted increased interest due to their high power density compared
to that of conventional capacitors [1].
Considerable efforts have been placed to develop new kinds of capacitive materials, such as
mixed metal oxides, carbon based materials (e.g. nanocarbons, carbon nanotubes, graphene)
supporting metal or metal oxides, conducting polymers combined with pseudocapacitive
materials. Coupling the unique advantages of nano-scale capacitive materials to form
nanocomposite electroactive materials is an important approach to control, develop and
optimize the structures and properties of electrode material for enhancing their performance for
supercapacitors. Recently, some bimetallic transition metal nanostructures have shown good
performances as electrodes in the energy devices [2], however, this promised structure has been
rarely exploited as a supercapacitor [3].
Here, we report the synthesis of advanced composite materials based on FeCo nanoparticles
coated by graphene to be used as supercapacitor electrodes. Among different techniques, one of
the methods to obtain controlled synthesis of carbon-coated nanoparticles is the Catalytic
Chemical Vapor Deposition (CCVD) of light hydrocarbons. Carbon-coated magnetic FeCo
nanoparticles were prepared by CCVD [4,5] of methane at atmospheric pressure.
To evaluate the quality and characteristics of the obtained products, the prepared nanomaterials
were carefully characterized by the combined use of micro-Raman spectroscopy, Scanning
Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), thermogravimetric
analysis coupled with mass spectrometer, X-ray diffraction.
For the electrochemical investigation, cyclic voltammetry (CV) and galvanostatic chargedischarge tests were performed using a potentiostat/galavanostat to evaluate the electrochemical
performance.
We found that our nanoparticles show an excellent pseudocapacitance properties and high
specific capacitances.
Keywords: Supercapacitors, Catalytic Chemical Vapor
Nanoparticles
Deposition, Graphene, FeCo
* Corresponding author: Eleonora Ponticorvo, [email protected]
References
[1] G. Wang, L. Zhang, J. Zhang, Chem. Soc. Rev. 41 (2012) 828
[2] N.A.M. Barakat, M. Motlak, A.A. Elzatahry, K.A. Khalil, E.A.M. Abdelghani, Int J Hydrog
Energy. 39 (2014) 305
[3] N.A.M. Barakat, A.G. El-Deen, G. Shin, M. Park, H.Y. Kim, Mater Lett. 99 (2013) 168
[4] W.S. Seo, J.H. Lee, X. Sun, Nat Mater. 5 (2006) 971
[5] M. Sarno, C. Cirillo, P. Ciambelli, Chem. Eng. J. 246 (2014) 27
97
INORG-03:Gold nanoparticles obtained by aqueous digestive ripening:their application as
X-ray contrast agents
Claudio Evangelisti1*, Laura Polito1, Alessandro Silvestri1, Giacomo Bellani2, Vanessa
Zambelli2, and Rinaldo Psaro1
1 - ISTM-CNR Istituto di Scienze e Tecnologie Molecolari, Milano, Italy
2 - Department of Health Science, University of Milano-Bicocca, Monza, Italy
Medical imaging has undergone enormous improvements due to the development of
nanomaterial-based contrast agents which are quickly becoming valuable and potentially
transformative tools to enhance medical diagnostics for a wide range of in vitro and in vivo
imaging modalities. In this context, gold nanoparticles (AuNPs) show interesting behavior as
computed tomography (CT) contrast agents owing to their high X-ray absorption coefficient,
low toxicity and high biocompatibility.[1]
Here, we report an novel protocol to synthesize large quantities and reproducible quality of
water soluble size-controlled PEGylated Au NPs (mean core diameter of 3.8 nm) (Scheme).[2]
The synthesis exploited a combination of gram-scale synthesis of Au NPs by MVS technique
and morphology control by digestive ripening process [3] in aqueous medium in the presence of
thiol ligands (i.e. PEG-SH).
The morphology and the structural
features of Au NPs were evaluated
by
transmission
electron
microscopy, inductively coupled
plasma-optical
emission
spectrometers,
UV-Vis
spectroscopy and dynamic light
scattering analysis. PEGylated Au
NPs were effectively used as CT
contrast agents for in vivo
experiments on mice. The surface
functionalization together with the
Scheme
small hydrodynamic diameters of
the
engineered
nanoparticles
permitted their efficient renal
clearance, still retaining a prolonged blood circulation and a stealth capability.
Keywords: Au NPs, digestive ripening, CT contrast agents
* Corresponding author: Claudio Evangelisti, e-mail contact: [email protected]
References
[1] E. Boisselier, D. Astruc, Chem. Soc. Rev. 38 (2009) 1759.
[2] A. Silvestri, L. Polito, G. Bellani, V. Zambelli, R.P. Jumde, R. Psaro, C. Evangelisti, J. Coll.
Surf. Interf. Sci. 439 (2015) 28.
[3] D. Jose, J.E. Matthiesen, C. Parsons, C.M. Sorensen, K.J. Klabunde, J. Phys. Chem. Lett. 3
(2012) 885.
98
INORG-04:New sustainable technology to recover returned concrete
Giorgio Ferrari
Mapei S.p.A., Via Cafiero 22, 20158 – Milano (Italy) - e-mail [email protected]
With an estimated production of 25 billion tons per year, concrete is the most used construction
material in the world. [1]. One of the most abundant waste in ready-mixed plants is returned
concrete, the unset concrete that comes back to the plant in the concrete truck as excess
material. This can be the small amount of concrete leftover at the bottom of the drum, or more
significant quantities not used by the costumer at the construction site. Returned concrete at
ready-mixed plant is about 5% of the overall production in the U.S. [2] and 2% in Japan [3]. In
Europe official data are not available, but a rate of 2% is considered a reasonable estimate in
Western Europe. No information is presently available for China and developing countries. On
the conservative hypothesis of an average rate of returned concrete of 1%, it can be estimated
that about 250 million tons are globally generated every year.
All the current methods to treat returned concrete generate waste to be disposed in the landfill.
In the present paper, a new method based on a new additive that transforms returned concrete
into aggregates for new concrete, is presented. The new technology permits the complete
recycling of returned concrete in an easy way, without any waste production. Furthermore, the
new technology reduces the consumption of natural aggregates, with significant benefits both in
terms of natural resource protection and economic saving.
The new additive is based on high molecular weight linear anionic polyacrylamide and
aluminium compound. When added to returned concrete, the new additive causes the
coagulation of the cement paste around the coarse aggregates, forming a granular material
consisting of a core formed by the original stone aggregates covered by a composite material
made by cement paste, sand and the additive.
Results of life cycle assessment (LCA) demonstrated that the new technology is by far less
impacting than the option of dumping of returned concrete and therefore contributes in reducing
the environmental impact of concrete production at the RMC plant, representing an important
contribution for concrete sustainability.
Keywords: Recycled aggregates, returned concrete, superabsorbent polymer, sustainability
References
[1] WBCSD, July 2009, The cement sustainability initiative: Recycling concrete [on-line].On:
www.wbcsdcement.org [Accessed February 4th, 2015]
[2] Obla, K., Kim, H. and Lobo, C., “Crushed returned concrete as aggregate for new concrete –
Final report”, RMC Research & Education Foundation, 2007
[3] Sato, Y., Oyamada, T. and Hanehara, S., “Applicability of sewage sludge ash (SSA) for
paving material: A study on using SSA as filler for asphalt mixture and base course
material”, Proceedings of the Third International Conference on Sustainable Construction
Materials and Technologies, Kyoto, Japan, 2013
99
INORG-05:Improving visible light active photocatalyst performances through photoactive
supports in the photocatalytic removal of emerging contaminants
Vincenzo Vaiano, Olga Sacco*, Diana Sannino, Paolo Ciambelli
Department of Industrial Engineering, University of Salerno, Via Giovanni Paolo II, 84084
Fisciano (Salerno), Italy
Environmental contamination by pharmaceuticals, personal-care products and pesticides is an
emerging issue. Even if emerging contaminants are present at very low concentrations in the
aqueous environment, they make implications for human health, giving rise to phenomena of
bacterial resistence. UV-photocatalytic treatments were successful to the complete
mineralization of various emerging pollutants; however the photoactivity is dependent by an
efficient irradiation of the photocatalyst surface. An improvement in the photon transfer was
found by coupling a photocatalyst with light emitting photoluminescent substances such as
phosphors. Indeed, phosphors have optically active centres that can absorb an incident
radiation, which is re-emitted at shifted specific wavelengths. The phosphors can act as
microradiators when present together with the photocatalyst capturing the radiation coming
from external light sources and emit their specific radiation in the proximity of photocatalysts.
Relevant photocatalytic activity of visible active N-doped TiO2 photocatalyst (NdT) coupling
with inorganic down-conversion (IP) and organic up-conversion phosphors (OP) [1], was
found. Several factors influence the photocatalytic performances, such as phosphors properties,
photocatalysts to phosphors ratio, structuring of photocatalysts, active photocatalyst load and
characteristics.
Results about the photocatalytic degradation of different emerging contaminants obtained under
UV or visible light irradiation on phosphors supported NdT will be shown, evidencing the
enhancement of photocatalytic degradation ability in comparison to only NdT photocatalyst.
Keywords: N-doped TiO2, up-conversion organic phosphors, photocatalytic degradation of
emerging contaminants
* Corresponding author: Olga Sacco, e-mail contact: [email protected]
References
[1] V. Vaiano, O. Sacco, G. Iervolino, D. Sannino, P. Ciambelli, R. Liguori, E. Bezzeccheri, A.
Rubino, Applied Catalysis B: Environmental 176 (2015) 594–600
100
INORG-06:Photocatalytic Properties of N-Doped TiO2 Functionalized Ceramic Tiles
under UV and Visible Light Irradiation
Giuseppe Sarno1*, Vincenzo Vaiano1, Paolo Ciambelli1, Diana Sannino1
1 - University of Salerno, Department of Industrial Engineering, Via Giovanni Paolo II, 132,
84084 Fisciano (Salerno), Italy
In order to use sunlight or visible light emitted by traditional lamps or LEDs in photocatalytic
reactions, the synthesis of visible light-active TiO2 is a promising feature. The surface
modification by doping with non-metal ion is an efficient method to improve the photocatalytic
activity of photocatalysts under visible light irradiation. To confer self-cleaning properties to
ceramic tiles, TiO2 is deposited on their surface; however these materials are effective only in
presence of UV light. For this reason, in this work, tiles functionalized with N-doped TiO2 have
been studied in the discoloration of aqueous solution of methylene blue (MB) in presence of
visible and UV light irradiation. Functionalized tiles were prepared by impregnation technique
using a TiO2 sol obtained using titanium isopropoxide, ethanol, acetyl acetone, acetic acid, urea
and PEG, followed by heat-treatment in air at 550°C. In order to obtain undoped TiO 2 the same
preparation was realized without urea. Photocatalytic tests were performed at ambient
temperature and atmospheric pressure using a steel reactor with a Pyrex window. The
irradiation of photoreactor was realized by four UV lamps or light emitting diodes (LEDs) with
an emission spectrum in the visible region. The initial concentration of MB was about 10 ppm.
In presence of UV irradiation, MB concentration decreases, with a similar reaction rate for
functionalized tiles with undoped and doped TiO2 film. In presence of visible light irradiation,
the decrease of MB concentration over tile functionalized with undoped titania is similar to that
obtained by the photolysis process, indicating that this sample is inactive for MB discoloration
under visible light irradiation. In contrast, the presence of N-doped TiO2 on ceramic tiles
showed higher discoloration rate with a complete disappearance of MB within 120 h. These
results clearly indicate that N-doped TiO2 film is able to exploit both UV and visible light
emitted by the light sources.
Keywords: N-doped TiO2, Ceramic Tiles, Visible light irradiation, self-cleaning, sol-gel
method.
* Corresponding author: Giuseppe Sarno, [email protected]
101
INORG-07:Monolithic nanoporous-crystalline aerogels with sulfonated amorphous
phases: fast and efficient polymer materials for removing VOCs from water
Vincenzo Venditto1, Marina Pellegrino1*, Gaetano Guerra1, Christophe Daniel1, Anna
Borriello2
1- Department of Chemistry, Nanomates Center and INSTM Research Unit, University of
Salerno, via Giovanni Paolo II, 84084 Fisciano (SA), Italy
2- Institute for Polymers, Composites and Biomaterials, CNR Italy, P.le Fermi,1 80055
Aerogels are generally obtained by drying of wet gels and constitute a unique class of materials,
which is characterized by highly porous networks. For many applications, it is relevant to obtain
monolithic aerogels, which are usually obtained with a large variety of chemically-crosslinked
polymers. A special class of monolithic physically-crosslinked polymeric aerogels, based on
thermoplastic polymers exhibiting nanoporous-crystalline forms (syndiotactic polystyrene, s-PS
and poly(2,6-dimethyl-1,4-phenylene)oxide, PPO), has been recently achieved [1]. These
nanoporous-crystalline polymeric aerogels, whose physical knots are constituted by
nanoporous-crystalline phases, exhibit beside disordered amorphous meso and macropores
(typical of all aerogels) all identical nanopores (or microporous according to IUPAC
classification) of the crystalline phases. Nanoporous-crystalline polymeric aerogels, although
characterized by high sorption capacity typical of the nanoporous crystalline phases (due to the
sorption of molecules as isolated guests of the host crystalline phase), associated with high
sorption kinetics typical of aerogels (due to the high and disordered porosity of the aerogels),
present poor water permeability. This strongly reduces water pollutant sorption kinetics and
constitutes a major drawback for their practical use for removal of VOC pollutants from water
and moist air. The selective sulfonation of the polymer amorphous phase is a possible solution
to this inconvenience.[2]
In this paper, preparation, characterization and VOCs sorption properties from water dilute
solution, of sPS and PPO monolithic aerogels having sulfonated amorphous phase, are
presented and compared.With respect to unsulfonated nanoporous-crystalline polymeric
aerogels, these new selectively sulfonated aerogels present a high water diffusivity and uptake.
Moreover, the sorption kinetics of VOCs water pollutants by the hydrophobic nanopores of the
crystalline phase, are greatly increased.
Keywords: nanoporous crystalline phase, sulfonated polymers, aerogel, water treatment.
* Corresponding author: Marina Pellegrino, e-mail contact: [email protected]
References
[1] a) C. Daniel, D. Alfano, V. Venditto, S. Cardea, E. Reverchon, D. Larobina, G. Mensitieri,
G. Guerra, Adv. Mater. 17 (2005) 1515. b) C. Daniel, S. Longo, S. Cardea, J.-G. Vitillo, G.
Guerra, RSC Advances 2 (2012) 12011.
[2] a) A. Borriello, P. Agoretti, L. Ambrosio, G. Fasano, M. Pellegrino, V. Venditto, G. Guerra,
Chem.Mater. 21 (2009) 3191. b) V. Venditto, M. Pellegrino, R. Califano, C. Daniel, A.
Borriello, L. Ambrosio, G. Guerra, G. ACS Appl.Mater. & Interfaces 7 (2015) 1318.
102
INORG-08: Flexible and Solvent Resistant Graphene Oxide Paper
Mario Maggio*, Maria Rosaria Acocella, Marco Mauro, Gaetano Guerra
Department of Chemistry and Biology and INSTM Research Unit, Università di Salerno,
84084 Fisciano (SA)
The ability of graphite oxide aqueous suspensions to form robust and resilient Graphene Oxide
(GO ) paper is largely improved by basification of the suspension prior of processing. In
particular, casting procedures, which are generally unsuitable for production of GO paper[1],
become suitable for the case of basified GO (b-GO) suspensions, leading to flexible freestanding papers. Thermal treatments of b-GO paper easily produce graphene oxide paper, i.e.
paper with exfoliated GO, while thermal treatments of GO paper lead to crumbled films with
partially exfoliated GO[2]. Differently from usual GO papers, papers from b-GO suspensions
exhibit remarkable resistance to solvents as well as to acids and bases, even in aqueous
solutions. Mechanical properties of b-GO paper are comparable or even better than those of
usual GO paper. In particular, paper flexibility, measured as minimum radius of curvature is
definitely higher for b-GO paper, when obtained by casting procedures.
Keywords: Film casting, degree of layers orientation, radius of curvature, thermal exfoliation
* Corresponding author: Mario Maggio, [email protected]
References
[1] Ruoff et al. Nature 2007, Vol 448.
[2] C. -J. Kim, W. Khan, S. –Y. Park, Chem. Phys. Lett. 511 (2011) 110–115
[3] A. Mathkar, D. Tozier, P. Cox, P. Ong, C. Galande, A. L. Reddy, P. M. Ajayan, J. Phys.
Chem. Lett. 3, (2012) 986-991.
103
ORG-01:Denatured Lysozyme: a new tool to solubilize carbon nanomaterials
M. Siepi 1*, D. M. Monti 2, E. Notomista1
1 - Department of Biology, University of Naples Federico II, Via Cinthia I, 80126, Naples
2 - Department of Chemical Sciences, University of Naples Federico II, via Cinthia I, 80126,
Naples
Carbon-based nanomaterials have generated great interest due their unique physical, electrical,
chemical and thermal properties [1]. However, carbon nanostructures are typically insoluble in
most solvents, especially in aqueous solutions. Many non-covalent and covalent modification
protocols have been developed to solubilize carbon nanostructures. These typically involve noncovalent adsorption of detergents or the introduction of chemical groups or linker molecules,
which can compromise the unique properties of the materials, as well as their biocompatibility
[2-3]. To overcome this limit, different strategies to optimize their surface functionality and
biocompatibility are needed. Integrating carbon nanomaterials with biological systems to form
hybrid functional assemblies is an innovative research area with great promise for different
applications [1]. To this aim we used denatured lysozyme (dLys) as biosurfactant to solubilize
carbon nanomaterials. To obtain dLys, the native protein was reduced and the exposed cysteines
were blocked by alkylating agents, with consequent exposure of two well known antimicrobial
regions located at the N- and C-termini. Each of these two regions behaves as an amphipathic
peptide with a highly charged positive surface and a hydrophobic surface exposing both
aliphatic and aromatic residues. In order to understand interactions between dLys and carbon
nanomaterials, we performed dLys CD spectroscopic analyses in presence of increasing
concentrations of TFE (1 to 50% v/v), which is expected to mimic carbon surfaces. dLys
showed an unordered structure, whereas, in the presence of TFE, the α-helical content increased
up to 48%. We then used dLys to solubilize multi-walled carbon nanotubes (MWNT) as well as
fullerene (C60). Complexes of dLys and MWNT were analysed by different techniques.
MWNT, solubilized by dLys, are unbundled, as indicated by UV-Vis spectroscopic analyses.
Moreover, we found a high and positive zeta-potential value, which indicated that MWNTs
were coated by dLys, since MWNTs z-potential in water is negative [4]. Microscopic
investigations by transmission electron microscopy (TEM) confirmed the existence of well
dispersed nanotubes. Finally, dLys were able to solubilize fullerene, forming carbon
nanoparticles. C60 solubilization was confirmed by UV–Vis spectroscopy. The C60/dLys
samples were analysed by dynamic light scattering experiments, TEM and atomic force
microscopy (AFM) which indicated that the solutions contain nanoparticles with size between
50 and 110 nm. The high and positive zeta potential value indicated that dLys is at the surface
of nanoparticles. These data demonstrate that dLys is a very promising tool to solubilize and
functionalize hydrophobic surfaces, thus opening the way to the obtainment of innovative
functional materials for the development new biomedical and electronic devices.
Keywords: carbon nanotubes, fullerene, denatured lysozyme
* Corresponding author: Marialuisa Siepi, [email protected]
References
[1] M. Calvaresi and F. Zerbetto, Acc Chem Res. 46 (2013) 2454-63
[2] R. Rastogi et all, Journal of Colloid and Interface Science. 328 (2008) 421-428
[3] H. Park et all, Nano Lett. 6 (2006) 916-9
[4] M. kojima et all, Nanoscale Research Letters. 6 (2011) 128
104
ORG-02:Pyrolysis of α-cellulose with multimode microwave oven
Damiano Bandelli1*, Mattia Bartoli1, Luca Rosi1,2, Alessio Giovannelli3, Piero Frediani1
and Marco Frediani1
1 - Università degli studi di Firenze, Dipartimento di Chimica “Ugo Schiff”, Via della
Lastruccia 3, S.Fiorentino (Fi)
2 - Consorzio Interuniversitario di Reattività Chimica e Catalisi (CIRCC), Via Celso Ulpiani
27, Bari, Italy
3 - CNR-IVALSA Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy
The end of fossil fuels era is becoming day by day however the request of raw materials and
fuels from industry is growing every year [1]. As a consequence the research for renewable
resource to supply oil is became very attractive [2]. Biomasses are very promising sources to
satisfy the growing request of energy and raw materials [3] and in the same time to reduce the
environmental impact due to their production [4]. Cellulose is particular interesting among
different available biomasses because it is not interfere with the availability of resource for
alimentation [5]. It is the main component of woody biomasses (until 50%) [6], and it is the
most abundant polysaccharide. α-cellulose was pyrolyzed using a multimode microwave oven,
different microwave absorbers and experimental set ups. Bio-oil was obtained with a maximum
of 37.6% using iron as MW absorber and set-up B. Using carbon as MW absorber a large
gasification of cellulose was reached (yield of gas up to 53.8%). A Biochar yield of 64.1% was
reached with use of Al2O3 and a very small gas production (3.0%) was observed. Dark brown
bio-oils were collected with low density and viscosity due to the presence of large amount of
furanosidic compounds. They were characterized through GC-MS, FT-IR, NMR. A GC-MS
procedure using calculated retention factor was employed to evaluate the composition of Biooils and to support a proposed mechanism through identification of intermediates present in biooils. A high concentration of levoglucosan (133.9 mg/mL) together with acetic acid, acetic
anhydride, 1-hydroxy-2-propanone, formic acid and furfural were obtained using graphite as
MW absorber. Water contents in bio-oils were affected by all parameters of the process, mainly
by the MW absorber. The use of silica has proved to be a promising way to obtain Bio-oil with
low content of water (13%), while pyrolysis in the presence of carbon a large amount of water
was formed (46 %).
Keywords: template, writing style, abstract
* Damiano Bandelli, [email protected]
References
[1] S.G. Bunker, Raw material and the global economy: Oversights and distortions in industrial
ecology, (1996).
[2] N.A. Utama, A.M. Fathoni, M.A. Kristianto, B.C. McLellan, Procedia Environmental
Sciences, 20 (2014) 40-45.
[3] P. McKendry, Bioresource Technology, 83 (2002) 37-46.
[4] Rafaschieri, A. et al. Energy Convers. Manage., 1999, 40, (14), 1477–1493, Fuel and
Energy Abstracts, 40 (1999) 397.
[5] A.J. Stamm, Wood and cellulose science, Wood and cellulose science., (1964).
[6] C.-F. Liu, R.-C. Sun, Chapter 5, Elsevier, Amsterdam, 2010, pp. 131-167.
105
ORG-03:Intrinsic antioxidant bio-based polymer for food active packaging
Stefano Antenucci
Luisella Verotta 2
1*
, Valentina Sabatini
1
, Hermes Farina 1, Marco Aldo Ortenzi
1
,
1 - CRC Materiali Polimerici (LaMPo) – Department of Chemistry, University of Milan, Via C.
Golgi 19, 20133 Milano, Italy
2 - Department of Chemistry, University of Milan, Via C. Golgi 19, 20133 Milano, Italy
Active packaging, used in pharmaceutical and food industries, is used for a number of different
purposes: one of its most common embodiments is the enhancement of the shelf-life of
products, slowing down the kinetic of degradation. The concept of “active packaging” is
relatively new, therefore it represents a small part of all industrial packaging production.
Nevertheless there is a lot of interesting on this technology both in academic and industrial
world: the amount of publication concerning “active packaging” has been dramatically
increasing in the last three years and also the food industry sees it as a way to lower the amount
of food wastes, estimated in 750 billion $/y[1].
One of the most important issues related to active packaging is that active substance can
migrate into food and affect its properties. In the present work a bio-based polymer has been
covalently linked to the “active” substrates in order to prevent any kind of migration. We used
poly(lactic acid) (PLA) due to its completely “green” feature and to its well-known industrial
synthesis. Active molecules suitable for the reaction with PLA are Tyrosol and Vanillyl
Alcohol[2].
The phenolic moiety gives the antioxidant feature to the molecule and the aliphatic hydroxyl
group makes these molecule able to react with lactide: in this way it is possible to obtain a
polymer with high molecular weight and an antioxidant moiety directly linked to chains that
cannot migrate. The rheological behavior of the material shows that the presence of functional
molecules decreases melt viscosities of materials due to the effect as chain initiator. This
detrimental feature can be overcome modifying the molecular architecture.
DPPH assay, a standard test used to evaluate the radical scavenging activity of a substance, has
been used to verify the antioxidant activity of the polymers. Pure vanillyl alcohol has a good
reducing activity, about 92% of scavenging, that is retained when it is linked to the polymer
whereas tyrosol shows a low activity (about 6%). Pure PLA and PLA with tyrosol do not have
an interesting activity.
Keywords: active packaging, poly(lactic acid), bioplastic
* [email protected]
References
[1] cost 099/14, active and intelligent fibre-based packaging - innovation and market
introduction (actinpak), 3(2014)
[2] B.B. Shyamala, M Madhava naidu, G Sulochanamma, and P. Srinivas, J. Agric. Food Chem.
(2007), 55, 7738–7743
106
ORG-04:Polyhydroxyalkanoate extraction from biomass using environmentally friend
techniques.
F. Galli 1,3, N. Frison2, S. Capelli 1, C. L. Bianchi1,3, F. Fatone2, C. Pirola 1,3
1 -Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi 19, 20133 Milano.
2 –Università degli Studi di Verona, Dipartimento di Biotecnologie, Strada Le Grazie 15,
37134 Verona
3 -Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, INSTM,
Currently, the typical polyhydroxyalkanoates (PHA) extraction procedure relies on the
solubilization of PHA using organic solvents, particularly chloroform [1]. Researches
developed extraction processes adopting more tolerable solvents like ethanol, cyclic carbonates
and acetone [2]. However, the use of these solvents raises some drawbacks. In particular, their
regeneration requires high amount of energy, generating costs and make the whole process less
sustainable. Moreover, the use of petroleum based-solvents like the cited above is against the
modern green chemistry theory, which aims to develop operations using water as solvent [3].
The object of this study is to select solvents able to reduce the energy requirements,
characterized by the least toxicity and with very limited safety impacts. For this reason, we
want to develop a suitable extraction method, based on the cell wall disruption using sodium
chloride and the PHA extraction using sodium hydroxide. Moreover our aim is to eliminate all
the steps that are critical for this separation, in particular the use of a centrifuge, because in a
medium-large scale extraction, the economic impact is not sustainable, increasing the whole
batch cycle time. We performed several experiments to determine the effectiveness of the
proposed method. In order to study the behavior of the biomass in alkali environment we started
to use different Biomass/NaOH ratio. Increasing the amount of NaOH used for the extraction,
the residues reduced to reach a plateau corresponding to the PHA quantity accumulated within
the. The pre-treatment in NaCl solutions was carried out before the NaOH one. The cells
concentration was fixed at 10 g/L while the concentration of NaCl at 0.2 g (biomass/g NaCl)
and incubated at 30°C for 3 h. We fixed the cell concentration at 10 g/L and treated with
different concentrations of NaOH at 30 °C for 2 h. We also made some extraction kinetic
studies at different biomass/NaOH ratios in order to investigate the time required to reach the
maximum solubility value of cell residues. The analyzed biomass contained 14.6% of PHA,
estimated with extraction in chloroform. Moreover, the use of ultrasound for the extraction of
PHA was studied changing between pulsed or continuous wave and varying the amount of
NaOH.
Keywords: polyhydroxyalkanoates, green extraction, NaOH, ultrasounds.
* Corresponding author: Federico Galli, [email protected]
References
[1] L.W. Lowell, W. K. Rohwedder, Environ. Sci. Tech., 8 (1974) 576
[2] M.H. Madkour, D. Heinrich, M.A. Alghamdi, I.I. Shabbaj, A. Steinbuchel,
Biomacromolecules, 14, (2013) 2963.
[3] R. A. Sheldon, Green Chem, 7, (2005) 267.
107
ORG-05:Guest activated organic functional materials
E. Macedi1, A. Meli,1 I. Izzo,1 F. De Riccardis,1 V. J. Smith,2 L. J. Barbour,2 and
C.Tedesco1*
1 - Dipartimento di Chimica e Biologia, Università degli Studi di Salerno, Fisciano, Italy
2 - Dept. of Chemistry and Polymer Science, University of Stellenbosch, Stellenbosch, South
Africa
Natural and synthetic macrocycles have been studied by researchers for their versatile
functions. Among them, cyclopeptoids show biostability and potential diversity, which make
them ideal building blocks for supramolecular architectures with novel chemical properties and
defined biological activities.
Peptoids and peptides differ by the position of the side chain, that is no longer bound to the αcarbon but to the nitrogen atom. Due to the lack of the amide proton, the formation of NH …OC
hydrogen bonds is prevented and weaker interactions such as CH …OC and CH-pi play a key
role.[1] Differently sized cyclopeptoids have been synthesized and characterized from Salerno‟s
group[2] and many biological activities have been demonstrated (transport across a phospholipid
membrane,[3] antifungal activity[4]).
Herein are reported examples of conformational flexibility, where the choice of the side chains
affects the solid state dynamic behaviour upon solvent uptake and release, making the
cyclopeptoid an acetonitrile activated material.
Figure 1. Single crystal-to-single crystal transformation for a cyclopeptoid upon loss and reuptake of acetonitrile
Research performed in agreement with the project POMOS, funded by EU in the framework of
the 7° People Program International Research Staff Exchange Scheme.
Keywords: cyclic peptoids, functional materials, inclusion compound
* Corresponding author: C. Tedesco, [email protected]
[1] C. Tedesco, L. Erra, I. Izzo, F. De Riccardis, CrystEngComm 16 (2014) 3667
[2] (a) N. Maulucci, I. Izzo, G. Bifulco, A. Aliberti, C. De Cola, D. Comegna, C. Gaeta, A.
Napolitano, C.Pizza, C. Tedesco, D. Flot, F. De Riccardis, Chem. Comm. (2008), 3927; (b) I.
Izzo, G. Iannello, C. De Cola, B. Nardone, L. Erra, G. Vaughan, C. Tedesco, F. De Riccardis,
Org. Lett. 15 (2013), 598
[3] C. De Cola, S. Licen, D. Comegna, E. Cafaro, G. Bifulco, I. Izzo, P. Tecilla, F. De
Riccardis, Org. Biomol. Chem. 7 (2009) 2851
[4] D. Comegna, M. Benincasa, R. Gennaro, I. Izzo, F. De Riccardis, Bioorg. Med. Chem. 18
(2010) 2010
108
ORG-06:Experimental and Finite Element optimization of the production process of
rubber insulated electric cables vulcanized with steam water
G. Milani1*, A. Galanti2, C. Cardelli3, F. Milani4, A.Cardelli3
1 - Technical University of Milan, Department ABC, Piazza Leonardo da Vinci 32, 20133,
Milan, Italy
2 - Mixer Compounds Spa, Via Chiara 6/C 48012 Villa Prati di Bagnacavallo (RA), Italy
3 - IPOOL Srl, Ripa Castel Traetti 1, 51100 Pistoia, Italy
4 - CHEM.CO Consultant, Via J.F.Kennedy 2, 45030 Occhiobello, Rovigo, Italy
The standard industrial process to produce medium voltage electric cables based on EPDM
consists in crosslinking by peroxides with high temperature steam (pressurized water vapor).
Suboptimal material crosslinking is usually due to drop of the design temperature along the
vulcanization pipe. Temperature variations are connected to variations of steam pressure into
pipe system.
A Genetic Algorithm (GA) approach is used in this paper to predict the final crosslinking
degree of a medium voltage electric cable crosslinked in four different conditions. The
crosslinking degree is experimentally obtained by means of DSC determination of not
decomposed peroxide from the external layer to the core of the cable insulation.
The final task is to minimize the difference between numerically predicted and experimentally
determined crosslinking degree using steam temperature profile along the pipe to explain the
variations.
The integrated numeric experimental approach allows optimizing the amount of peroxide in the
compound and comparing the performances of different peroxide mixtures.
Crosslinking degree compliance should be obtained as a function of the temperature gradient
measured in the steam pipe.
Production conditions could be automatically calculated according to the cable parameters
increasing quality reliability and reducing scraps..it
Keywords: power cables production lines; EPR, EPM, EPDM elastomers; peroxide
vulcanization; steam curing; Optimization
* Corresponding author: Gabriele Milani, e-mail: [email protected]
References
[1] G. Milani, A. Galanti, C. Cardelli, F. Milani, A. Cardelli, Combined numerical Finite
Element and experimental optimization approach in the production process of medium voltage
rubber insulated electric cables vulcanized with steam water. Part 1: DSC and rheometer
experimental results. Rubber Chemistry and Technology (2015) In press.
[2] G. Milani, F. Milani, Combined numerical Finite Element and experimental optimization
approach in the production process of medium voltage rubber insulated electric cables
vulcanized with steam water. Part 2: Numerical simulations and inverse analyses. Rubber
Chemistry and Technology (2015) In press.
109
The impact of hazardous substances in the case of structural failure of oil and gas offshore
platform
Anna Basco1*, Ernesto Salzano2
1 – AMRA - Center for the Analysis and Monitoring of Environmental Risk, Via Nuova Agnano
11, 80125 Naples, Italy
2 – Institute of Research on Combustion, CNR, Via Diocleziano 328, 80125 Napoli (IT)
Due to the recent events in Mexico (Deepwater Horizon, 2010), and the worldwide awareness
on climate change, which has increased the natural hazards and the occurrence of extreme
events [1], the European Union has set up, on January 2012, the Offshore Oil and Gas
Authorities Group, which is aimed at reducing the occurrence of major accidents related to
offshore oil and gas activities and to limit their consequences, thus increasing the protection of
the marine environment and coastal economies against pollution as well as limiting possible
disruptions to indigenous energy production in the Union, and at improving the response
mechanisms in case of an accident.
The impact assessment on coastline, sea environment and workers of an offshore loss is not the
scope of this work. Besides, several other chemicals – either during the normal functioning or
for post-event emergency, as chemical dispersant – are adopted on platforms for oil and gas
extraction and treatment. These chemicals can represent an added, severe hazard for the
environment in the case of structural failure of the platform but their choice is essentially based
on maximum efficiency, economical reason and productivity, with no reference to their impact
on environment.
A simple approach to this issue could be given by the Seveso Directive 96/82/EC (and
following legislation), which however does not apply to the offshore sector. Indeed, the Seveso
Directive is essentially based on the magnitude of accidental scenario, which in turn is based on
the amount of hazardous materials classified by CLP regulation.
This work tries to give new indications for the definition of chemical hazard on offshore
platform and has been developed within the project ARGO, financed by the Italian Minister of
Economic Development and lead by AMRA, Center for the Analysis and Monitoring of
Environmental Risk, aimed at defining Key Performance Indicators (KPI) for the impact
assessment of offshore platform located on the Adriatic Sea, with specific reference to extreme
natural events.
Keywords: Key Performance Indicator, Safety, Impact Assessment, Climate change, Offshore
platfom
* Corresponding author: dr. Anna Basco, [email protected]
References
[1] E. Salzano E., A. Basco, V. Busini, V. Cozzani, E. Renni, R. Rota, Public Awareness
Promoting New or Emerging Risk: Industrial Accidents Triggered by Natural Hazards, J Risk
Res 16 (2013), 46
110
ELENCO DEI PARTECIPANTI
Maria Rosaria
Sara
Stefano
Claudia
Finizia
Damiano
Claudia
Caterina
Anna
Federico
Elisa
Giovanna
Daniela
Marcello
Luigi
Fabrizio
Andrea
Fabio
Paolo
Claudia
Claudia
Amilcare
Alberto
Matteo
Chiara
Fabio
Chiara
Christophe
Antonio
Claudio
Francesco
Almerinda
Rocco
Martino
Giuseppe
Acocella
Andreoli
Antenucci
Antonetti
Auriemma
Bandelli
Bandinelli
Barzan
Basco
Bella
Bertolucci
Capuano
Caracciolo
Casa
Cavallo
Cavani
Chiminazzo
Chiozza
Ciambelli
Cioce
Cirillo
Collina
Comazzi
Compagnoni
Costabile
Curto
Dalla Valle
Daniel
De Nicola
De Rosa
Della Monica
Di Benedetto
Di Girolamo
Di serio
Di Silvestro
UniSA
UniBO
UniMI
UniPI
UniNA
UniFI
UniBO
UniTO
CNR NA
PoliTO
UniPI
UniMI
SSIP
UniSA
UniSA
UniBO
UniVE
MAPEI
UniSA
UniNA
UniSA
MAPEI
UniMI
UniMI
UniSA
MAPEI
UniPD
UniSA
UniSA
UniNA
UniSA
UniNA
UniNA
UniNA
UniMI
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
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[email protected]
[email protected]
[email protected]
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111
Roberto
Claudio
Amir Reza
Laura
Giorgio
Ivan
Nunzia
Federico
Simone
Alfonso
Lorenzo
Elena
Gaetano
Matteo
Giovanni
Giuseppina
Mariagrazia
Giorgio
Paola
Rosita
Oliva
Eleonora
Rodolfo
Mario
Anna
Francesco
Andrea
Mario
Massimiliano
Emanuela
Esposito
Evangelisti
Fahami
Falivene
Ferrari
Fuso Nerini
Galdi
Galli
Galliano
Grassi
Grazia
Groppo
Guerra
Guidotti
Iannaccone
Iervolino
Iuliano
La Sorella
Lanzafame
Lapenta
Leone
Macedi
Mafessanti
Maggio
Malafronte
Malara
Malmusi
Marchionna
Mari
Mastronardo
Valentina
Michele
Mattia
Federica
Gabriele
Candida
Placido
Medri
Melchionna
Melloni
Menegazzo
Milani
Milone
Mineo
UniNA
CNR MI
PoliMI
UniSA
MAPEI
VINAVIL
UniSA
UniMI
UniTO
UniSA
UniBO
UniTO
UniSA
CNR MI
PoliMI
UniSA
UniSA
UniVE
UniME
UniSA
UniSA
UniSA
UniBO
UniSA
UniNA
CNR MI
UniBO
SAIPEM
UniBO
UniME
CNR
(Faenza)
UniTS
UniBO
UniVE
PoliMI
UniME
UniCT
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
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112
Biagio
Annarita
Alberto
Lucia
Naviglio
Noschese
Olivo
Paciello
Elettra
Claudio
Francesco
Carlo
Paolo
Eleonora
Rinaldo
Andrea
Fabrizio
Francesco
Papa
Pellecchia
Pignataro
Pirola
Pollesel
Ponticorvo
Psaro
Pucci
Puleo
Puzzo
Raspolli
Galletti
Rizzo
Rombi
Rossetti
Ruggeri
Ruiz de
Ballesteros
Russo
Sabatini
Sacco
Salvini
Sannino
Santillo
Sarno
Scarso
Schiaroli
Scoti
Scudieri
Selleri
Siepi
Strukul
Annamaria
Paola
Elisabetta
Ilenia
Maria Pia
Odda
Vincenzo
Valentina
Olga
Antonella
Diana
Chiara
Giuseppe
Alessandro
Nicola
Miriam
Carmela
Tommaso
Marialuisa
Giorgio
Staz. Sper.
industria
pelli
UniSA
UniVE
UniSA
CNR
Faenza
UniSA
MAPEI
UniMI
ENI
UniSA
ISTM CNR
UniPI
CNR PA
UniBO
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
cpellecchia
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
UniPI
UniSA
UniCA
UniMI
PoliMI
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
UniNA
UniNA
UniMI
UniSA
UniFI
UniSA
UniNA
UniSA
UniVE
UniBO
UniNA
UniSA
PoliMI
UniNA
UniVE
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
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113
Oreste
Riccardo
Alfonso
Rosa
Angelo
Vincenzo
Vincenzo
Sesto
Rosa
Carla
Tarallo
Tesser
Troisi
Turco
Vaccari
Vaiano
Venditto
Viticoli
Vitiello
Zannoni
UniNA
UniNA
UniSA
UniNA
UniBO
UniSa
UniSA
AIRI
UniNA
ENI
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
[email protected]
114

XIX Congresso Nazionale Divisione di Chimica Industriale della

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