RELEVANT LEARNINGS FROM COST Acÿon D36 Molecular

Transcription

Catalytic Spectroscopy Laboratory
RELEVANT LEARNINGS FROM COST Ac1on D36
Molecular structure‐performance rela1onships at the surface of func1onal materials
Miguel A. Bañares
Insitute for Catalysis, CSIC, Madrid, SPAIN
Miguel A. Bañares
Ins1tuto de Catálisis y Petroleoquímica
Cataly2c Spectroscopy Laboratory
Cataly&c Spectroscopy Laboratory
miércoles 6 de abril de 2011
European Cooperation in the field of Scientific and Technical Research
www.cost.esf.org
Molecular Structure-Performance Relationships at
the Surface of Functional Materials
D36
Start date: 2006
End date: 2011
Miguel A. Bañares
Chair
CSIC / Spain
COST is supported by
the EU RTD Framework Programme
ESF provides the
COST Office through an EC contract
D36
www.cost.esf.org
Main objective
The main objective is an increase of the fundamental
understanding of the chemistry occurring at surfaces
and interfaces and the factors that tune it.
ESF provides the
D36
www.cost.esf.org
Bulk vs. Surface - Functional materials
safety, handling
ESF provides the
D36
www.cost.esf.org
Surface interaction
safety, handling
ESF provides the
D36
www.cost.esf.org
Surface interaction
safety, handling
ESF provides the
D36
www.cost.esf.org
Surface interaction
safety, handling
ESF provides the
D36
www.cost.esf.org
Surface interaction
Operation may transform the structures:
advanced “in situ” characterization methodologies that “look” at the functional
materials while they are working
safety, handling
ESF provides the
SAR ‐ Structure‐ac1vity rela1onships
Who is doing what? The n‐par1cle or n‐structure? Nanoparticles may help expose faces with specific properties and particle
size is critical for several applications
We want the properties of a nanoparticle without the hassle of a
nanoparticle:
- safety: exposure,
... problems grow when particles size shrinks
Miguel A. Bañares
- handling/operation ... not easy
Is it the nanoparticle or the nanostructure?
--> immobilization
--> generate the nanostructure at the surface of microscaled materials
–– minimize exposure ...
NANOPARTICLE IMMOBILIZATION vs. GENERATING NANOSTRUCTURED SURFACE
Miguel A. Bañares
- immobilization:
- entrapment would be safest,
but limited to some applications: optical, magnetic, ...
not for catalysis, sensing, ... surface properties
- need an immobilization that respects surface properties
- support-nP interaction has an effect ...
the property I need
the safety/convenience I need
Sensing, catalysis, ...
microparticles, polymers, matrix, tile,
chip, ...
Miguel A. Bañares
- immobilization:
- entrapment would be safest,
but limited to some applications: optical, magnetic, ...
not for catalysis, sensing, ... surface properties
- need an immobilization that respects surface properties
- support-nP interaction has an effect ...
the property I need
the safety/convenience I need
Sensing, catalysis, ...
microparticles, polymers, matrix, tile,
chip, ...
Entrapment
Entrapment
Miguel A. Bañares
Entrapment
Entrapment
Entrapment
Safest
Not for surface-related properties
Miguel A. Bañares
Entrapment
Entrapment
Entrapment
Surface interaction
Safest
Miguel A. Bañares
Entrapment
Entrapment
Entrapment
interface
n-particle
Surface interaction
Safest
Miguel A. Bañares
Entrapment
support
Entrapment
Entrapment
interface
n-particle
Safest
Miguel A. Bañares
Entrapment
support
Surface interaction
Nanoparticle-support interaction
- CHANGES
- TUNES
- CANCELS
- CREATES ..... properties
Entrapment
Entrapment
Support‐nanopar1cle interac1on
TUNING INTERACTION TO MODULATE PROPERTIES
Tangential
Miguel A. Bañares
Incipient interface interaction
Interfase
Extensive solid-state reaction
Supported or immobilized nanopar1cles
SYNTHESIS
EVEN DISTRIBUTION OF NANOPARTICLES ON LARGER
MICROPARTICLES -- HIERARCHICHAL NANODISPERSION
CHARACTERIZATION
VERY SUBTLE CHANGES HAVE TO BE ASSSESSED IN
STRUCTURE AND IN PROPERTIES
Miguel A. Bañares
MODELING - DESCRIPTION
TO UNDERSTAND/PREDICT PROPERTIES
Co3O4 nanoparticles on
Al2O3 microparticles
PCT/ES2009/070299
Glycerol carbonate
Products
O
||
Biological process
(DMC, enzyme)
O
O
H
O
|
O
H
O
|
H
O
|
Miguel A. Bañares
Glycerol carbonate
H
O
|
H
O
|
Glycerol
Glycidol
Supercritical process
(CO2)
Epoxi resins
Glycerol carbonate
Products
O
||
Biological process
(DMC, enzyme)
O
O
A
E
R
H
O
|
Miguel A. Bañares
U
H
O
|
H
O
|
Glycerol
H
O
|
O
Glycerol carbonate
Glycidol
Supercritical process
(CO2)
Epoxi resins
H
O
|
Miguel A. Bañares
Hierarchically dispersed Co3O4 NPs on ZnO micropar1cles
F. Rubio-Marcosa, V. Calvino-Casilda, M.A. Bañares, J.F. Fernandez,
Journal of Catalysis 275 (2010) 288–293
JF Fernández, F Rubio Marcos, V Calvino Casilda, M A Bañares Gonzalez
ES patent P201031234
Miguel A. Bañares
Glycerol carbonate selec1vity 96% at 69% glycerol conversion
Miguel A. Bañares
Miguel A. Bañares
Catalyst treatment
Miguel A. Bañares
Raman spectra reveal support interac1on
Miguel A. Bañares
Miguel A. Bañares
Miguel A. Bañares
Miguel A. Bañares
Miguel A. Bañares
Miguel A. Bañares
Glycerol carbonyla1on to glycerol carbonate
URETHANE
CARBONATE
Miguel A. Bañares
GLYCEROL
URETHANE
CARBONATE
Miguel A. Bañares
GLYCEROL
URETHANE
CARBONATE
Miguel A. Bañares
GLYCEROL
Operando Raman‐MS and GC cell
Mass spectrometry
Catalyst bed
Miguel A. Bañares
Gas Chromatography
Raman spectrometer
Reac1on
Gas inltet Reac1on oven
heated up to 600ºC
©M.A.Bañares
Thermocouple
OPERANDO methodology: Spectra are taken
during cataly1c reac1on, and reac1on products are analyzed simultaneously on line (Miguel A. Bañares, ICP‐
CSIC, Madrid). Cataly&c Spectroscopy Laboratory
NANOPARTICLES GENERATED DURING REACTION
Operando Raman‐GCduring propane ammoxida1on Miguel A. Bañares
Operando Raman-GC show that molecularly dispersed VOx and SbOx
aggregate into VSbO4 nanocrystals
Guerrero and Bañares, Chem. Commun.
modeli
modeli
modeli
Propane ammoxida&on runs great
Ethane ammoxida&ons does not run
Miguel A. Bañares
Alkane + NH3
Nitrile
Rojas, Calatayud, Guerrero, Bañares, Catal. Today (2010)
the surface
Nanopar1cles
property related to nanostructured surface
nanoparticles vs. nanostructured surface
Immobilization is an approach:
Support:
KEEPS
CHANGES
CREATES
PROPERTIES
PROPERTIES
NEW PROPERTIES
Miguel A. Bañares
But the properties or nanoparticles are in part due to their
nanostructured surface ...
... there is a need to understand nanostructure effect on
particles of any size (nano, micro, ...)
THE SURFACE IS THE KEY PERFORMER
Nanoparticles form during treatment
Nanoparticles vs. nanostructured surfaces
calcium
Glycerol oligomeriza1on over solid base catalysts
Agnieszka Ruppert, Monica Calatayud, Bert Weckhuysen
Utrecht University, the Netherlands
Universitè P.M. Curie, France
Glycerol oligomeriza2on: Catalyst Ac2vity
Na2CO3
homogeneous
catalyst
• CaO‐C: higher surface area material (BET 54 m2/g)
• conversion increased, selec1vity maintained
Conversion aaer 20 hours of reac1on. Ar, 220oC; no solvent
Na2CO3
homogeneous
catalyst
Na2CO3
homogeneous
catalyst
CaO catalysts
Preparation
CaO-A
from Ca(NO3)2
CaO-B
from Ca(OH)2
CaO-C
from Ca via Ca(OMe)2
CaO-A
CaO-B
CaO-C
SEM images, magnification 80.000 X
A.M. Ruppert, B.M. Weckhuysen Patent EP1961726A1, NWO (Aspect)
Modelling the systems
geometry of the interaction
• strength of the interaction
• deprotonation of the molecule
•
- comparison of MO (M=Mg, Ca, Sr, Ba) surfaces
- defects: stepped CaO surface
AIM : structure-reactivity relationship
Regular (001) surface
MgO
long
BaO
3.00
3.41
3.67
3.96
dlong Å
4.25
4.82
5.20
5.60
√2×√2 area Å2
36.15
46.49
54.00
62.69
θ molec/nm2
2.77
2.15
1.85
1.60
rt
1×1
SrO
dshort Å
√2×√2
o
h
s
CaO
coverage θ=1/4 molecules/
surface M
MgO
CaO
SrO
BaO
Basicity and dissociation
Surface + glycerol → surf+gly
Eads > 0 exothermic
4.00
best mode
3.50
3.00
2.50
• glycerol absorp1on on (001) surfaces of MgO, CaO, BaO, SrO studies
2.00
1.50
• same empirical glycerol conversion (MgO < CaO < SrO < BaO)
1.00
0.50
0.00
MgO
CaO
SrO
BaO
M. Calatayud, A. M. Ruppert, B. M. Weckhuysen Chem. Eur. J. 15 (2009) 10864
Eads > 0 exothermic
4.00
best mode
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
Almost not
dissociated
MgO
CaO
Partially
dissociated
SrO
BaO
Partially
dissociated
Fully
dissociated
Eads > 0 exothermic
4.00
best mode
3.50
2nd best mode
3.00
2.50
2.00
1.50
1.00
0.50
0.00
Almost not
dissociated
MgO
CaO
Partially
dissociated
SrO
BaO
Partially
dissociated
Fully
dissociated
Stepped CaO surface
• (501) plane
• different starting points
relaxed
frozen
coverage θ=1/10
molecules/surface M
Geometry of adsorption
Glycerol adsorbs as an extension of the step
Geometry of adsorption
Glycerol adsorbs as an extension of the step
Activity and dissociation
Eads > 0 exothermic
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
MgO
CaO
SrO
BaO
CaO
step
Step is more basic
Almost complete deprotonation
Activity and dissociation
Eads > 0 exothermic
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
MgO
CaO
SrO
BaO
CaO
step
Step is more basic
Almost complete deprotonation
Mechanism involving Lewis sites
Ca atom may activate the OH as
leaving group
Conclusions .... for catalysis people
Glycerol oligomeriza2on: conclusions
• Ac1vity of low‐surface area basic oxide materials parallels their basicity: BaO > SrO > CaO > MgO
• CaO can be made more reac1ve than Na2CO3 and BaO provided the right prepara1on method is applied
• CaO‐based materials containing the right balance of Lewis acid and basic sites possess very high ac1vity in the selec1ve etheriﬁca1on of glycerol towards di‐ and triglycerol.
• CaO colloidal par1cles are highly ac1ve in glycerol oligomeriza1on
Conclusions .... revisited
⇒ Defects play a key role in the reactivity of the material
⇒nanostructure
Aalto Univeristy, Finland
Univ. Pierre et Marie Curie Paris 06, France
• Stability of Hydroxylated (1h11) and (1h01) Surfaces
of Monoclinic Zirconia: A Combined Study by DFT and
Infrared Spectroscopy
• Structure and Stability of Formates and Carbonates
on Monoclinic Zirconia: A Combined Study by Density
Functional Theory and Infrared Spectroscopy
• Korhonen, Calatayud and Krause
• FINLAND AND FRANCE
The formation of formates and (bi)carbonates was studied on hydrated monoclinic zirconia. Comparison of the
adsorption energies suggested that the favored structures for the formates and bicarbonates on zirconia are of
bridged type. Additional support for these structures was provided by the good agreement between the calculated
vibrational frequencies and the vibrational frequencies observed by in situ DRIFTS. The adsorption energies further
suggested that the terminal hydroxyl groups are more reactive than the 2-fold coordinated species
Korhonen, Calatayud, Krause, J. Phys. Chem. C, 112(2008)16096
Korhonen, Calatayud, Krause, J. Hpys. Chem. C 112 (2008) 6469
V alkali
ESF provides the
V alkali
ESF provides the
V alkali
ESF provides the
V alkali
ESF provides the
Alkali dopants on structure, reducibility and
Raman spectra of vanadia‐1tania catalysts
Another model: MOH adsorption
•! More realistic: catalysts are often prepared by impregnation of alkali
hydroxyde.
•! It avoids the reduction of the surface by adsorption of a neutral
atom:
M ! M+ + 1eV5+ + 1e- !V4+
M
V1
Miguel A. Bañares
O
O
•!
•!
M+
around vanadia oxygen sites
OH- on surface Ti
M
V1
V2
•!
Oxygen sites now in the model:
V=O, V-O-V, V-O-Ti, OH
Catalytic Spectroscopy Laboratory
M
V1
Miguel A. Bañares
O
M
V1
Miguel A. Bañares
O
Summary
SAR: structure relationships, depend on the surface structure
Nanoparticles properties can be obtained via nanotextured surfaces
Exposure of nanoparticles can be minimized by support immobilization
Support effect: change/modify/create-new properties
Miguel A. Bañares
SYNTHESIS - controlling production, properties, scalable
UNDERSTANDING - in situ/operando characterization vs. modelling
... we can asses reactivity under different conditions, this may be used to
assess/tune toxicity
Acknowledgments
Support from the Spanish Ministry of Science and Innovation
“Subprograma de Fomento de la Cooperación Científica Internacional”
25
ESF provides the

RELEVANT LEARNINGS FROM COST Acÿon D36 Molecular

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