La Química y la alta tecnología. Materiales inteligentes Nazario Martín

Nazario Martín
Departamento de Química Orgánica.
Facultad de Ciencias Químicas
Universidad Complutense de Madrid
La Química y la alta tecnología.
Materiales inteligentes
Los avances de la química y su
impacto en la sociedad
CSIC, Madrid
25 de marzo de 2009
IUPAC name of [60]Fullerene
Hentriacontacycle [29.29.0.0.02,14.03,12.04,59.05,10.06,59.07,55.08,53. 09,21. 011,20.
013,18. 015,30. 016,28. 017,25. 019,24. 022,52. 023,50. 026,49. 027,47. 029,45. 032,44. 033,60. 034,57.
035,43. 036,56. 037,41.038,54.039,51.040,48.042,46]hexaconta-1,3,5(10),6,8,11,13(18),14,16,
19,21,23,25,27,29(45),30,32(44),33,35(43),36,38(54),39(51),40(48),41,46,49,52,55,
57,59-triacontaene
[5,6]-Fullerene-60-Ih
The fascinating forms of carbon
C60
C240
C540
Graphite
Multiwall carbon
Nanotubes (MWNTs; 1991)
Diamond
Singlewall carbon
Nanotubes (SWNTs;
1993)
Fullerenes (1985)
Graphenes
J. Mater. Chem. 2008, 18, 1415-1592
Special issue on Carbon Nanostructu
The fascinating forms of carbon
Carbon nanoonions
Nanohorns
Peapod
s
C60@C240@C540
5 nm
“The Nanoforms of Carbon“
J. Mater. Chem. 2008, 18, 1417 - 1426
The fascinating forms of carbon
Nanocups
Nanobuds
Nanotorus
J. Mater. Chem. 2008, 18, 1417 - 1426
Theme issue: Carbon Nanostructures J. Mater. Chem. 2008, 18,
1415-1592
Producción de Fullerenos
Vaporización con láser y expansión supersónica
Descarga de arco eléctrico en atmósfera inerte
Síntesis de Fullerenos en combustiones
Fullerenos formados naturalmente
¿Qué propiedades tienen los fullerenos?
Fullerenes: Superbencenos o superpolienos?
Isolated Pentagon Rule
Aromaticidad en el Benceno
1.40 Å
Propiedades físicas del C60
1.45 Å (5-6)
1.37 Å (6-6)
ΔHºf = 545 Kcal/mol
ρ = 1.78 g/cc
χ = -260 cgs ppm
Sublima por encima de 500 ºC a 10-7 torr
Alternancia de enlaces: 1.37 y 1.45 Å
The beginning …
(Resembling the attitude of a
scientist in front of the new
Fullerene ball)
Today…
(A good control
on the basic concepts)
Size
100
millions
100
millions
d ~ 1 nm
An appropriate molecule for the development of nanoscience
and nanotechnology but still looking for real applications…
Size
Photovoltaics
represents one of the
most realistic
applications of
Fullerenes !!!
100
100
millions
millions
d ~ 1 nm
An appropriate molecule for the development of nanoscience
and nanotechnology but still looking for real applications…
Renewable Energies
Renewable Energies
National Geographic,
June, 2004
Renewable Energies
Eolic energy
Biomass
Hydroelectric energy
Solar energy
Geothermal
energy
Solar Map
Photosynthesis
H2O
H
OH
Energy and
HO
HO
electron transfer
CO2
Luz
HO
H
H OH
OH
H
O2
Photosynthesis
H2O
H
OH
Energy and
Luz
HO
HO
HO
H
H OH
OH
H
electron transfer we can:
Mimicking
photosynthesis
Mimicking
COphotosynthesis we can:
2
••Harvesting
Harvestingsolar
solarenergy
energy
••Transform
it
into
chemical
Transform it into chemicalor
or
electrical
power
electrical power
••Problems
Problemssuch
suchas
aslack
lackof
ofenergy,
energy,
water,
foods,
environment
etc
water, foods, environment etccould
could
be
solved...
be solved...
O2
Photoinduced Electron Transfer (PET)
e─
●+
Donor
●─
Acceptor
100% Quantum yield
ARTIFICIAL PHOTOSYNTHETIC SYSTEMS
Las molécula imitan el proceso de la Fotosíntesis.
Transferencia electrónica fotoinducida
Estado excitado
E
hν
e-
D*
A
D+
hν
D
A
A-
Estado de separación
de cargas
Types of organic solar cells (II)
d) Bulk heterojunction. Conducting polymers
Al
ITO
OR
Plastic foil
n
RO
h+
eAlkoxy-PPV
Cyano-PPV
CN
n
Fabrication of PV devices (I)
a) Three layers
b) Four layers
Al
Al
D / A material
D / A material
ITO
Plastic foil
- PEDOT:PSS. Improves the contact in the interface
between the active phase and the ITO electrode
Al
- LiF. Makes unlikely that recombination of charges
happen after charge transfer
LiF
D / A material
Plastic foil
ITO
Plastic foil
c) Five layers
PEDOT-PSS
PEDOT-PSS
ITO
Plastic Organic Solar Cells
OR
RO
eOR
RO
OR
RO
Ultrafast PET
ITO
Metallic
electrode
hν
Transparent
substrate
F. Wudl, A. Heeger et al. Science, 1992
Bulk heterojunction. Conducting polymer as donor and C60 as acceptor
Al
ITO
OR
Plastic foil
RO
n
h+
eAlkoxy-PPV
Fullerenes
OMe
O
PCBM
Bulk heterojunction. Conducting polymer as donor and C60 as acceptor
• Inorganic PV devices show
η of around 30 %
• Organic PVs show a better mechanic
flexibility and lower production costs.
η = 2.5 %
O
CO2Me
O
O
O
PCBM
MDMO-PPV
Architecture of an organic solar cell
p-n heterounion
Cathode
Ionic interphase(LiF)
e-
Active phase (D+A)
PEDOT-PSS
h+
Anode (ITO)
Substrate
Transparent by
doping and
EHOMO~EHOMO (D)
C. J. Brabec et al. Adv. Funct. Mater 2001, 11, 15;
S. Günes et al. Chem. Rev. 2007, 107, 1324
Bulk heterojunction (BHJ)
n
Organic Solar Cells: How does it work?
Bulk-Heterojunction Diodes
Photon
Electronic
Transport
Hole
Transport
e- h+
Anode
Cathode
Electric Field
Efecto PV en heterounión
LUM
O
LUM
O
e
ITO
donor
acceptor
HOM
O
HOM
O
ÔEfecto fotovoltaico en heterounion p-n
- Absorción de luz
- Formación del excitón y transferencia electrónica
- Movilidad de los transportadores de carga
Bulk heterojunction.
Conducting polymer as donor and C60 as acceptor
Al
ITO
R
P3HT
Plastic foil
S
n
e
C6H13O
OC6H13
Polythiophene
Fullerenes
4c
DPM-12
Adv. Funct. Mater. 2005, 15, 1979
Photovoltaic cells from DPM-12: Optimization studies
R
a
Material
JSC
[mA cm-2]
VOC
[V]
FF
ηAM 1.5
[%]a
MDMO-PPV:DPM12
(1:4)
1.3
0.96
0.28
0.3
MDMO-PPV/ PCBM
(1:4)
4.17
0.83
0.52
2.28
P3HT:DPM-12 (1:4)
2.55
0.60
0.49
0.95
P3HT:DPM-12 (1:2)
4.74
0.65
0. 58
2.3
P3HT/PCBM (1:2)
6.5
0.55
0.50
2.2
P3HT
S
n
at 78 mW/cm2 white light intensity
e
C6H13O
OC6H13
4c
DPM-12
Energy Conversion
Efficiency of 2.3%
Adv. Funct. Mater. 2005, 15, 1979
The future of organic solar cells?
Silicon photovoltaic solar cells
The difference between
chemists and physicists:
"C60"
"C60"
Synthetic chemists
at the end of the day
Physicist who works
with chemicals,
at the end of the day
En cualquier caso, las moléculas son las
protagonistas. Cuando sean consideradas por la
sociedad en su justa medida, la química perderá
su mala imagen y podrá ser reconocida como
una forma más de expresión de la creatividad
humana.
hν
e-