V. Artero Y. Oudart A. Fihri S. Canaguier A. Legoff Hydrogen: Water, Sun and Catalysts Marc Fontecave Laboratoire de Chimie et Biologie des Métaux, Université Joseph Fourier, CNRS, CEA/DSV/iRTSV CEA-Grenoble 17 rue des martyrs 38054 Grenoble cedex 9, France [email protected]; Phone: (0033)438789103 ; Fax: (0033)438789124 Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05
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V. ArteroY. OudartA. FihriS. CanaguierA. Legoff
Hydrogen: Water, Sun and Catalysts
Marc FontecaveLaboratoire de Chimie et Biologie des Métaux, Université Joseph Fourier, CNRS, CEA/DSV/iRTSV
CEA-Grenoble 17 rue des martyrs 38054 Grenoble cedex 9, [email protected]; Phone: (0033)438789103 ; Fax: (0033)438789124
Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05
Doubling of the energetic supply in 40-50 years-World population increase(2050 from 6 to 9 billions)-economical growth
Limitation of the emission of green-house effect CO 2.
Limitation of the fossil sources of energy (petrol, gas, coal) coal: 200 years; gas: 100 years; oil: 50 years. Uranium: < 100 years, (surgenerators 300 years).
Need for new fuels from renewable sources
Energy global consumption(Total 13.5 TW)
Gas Hydro Renew
4.52
2.7 2.96
0.286
1.21
0.2860.828
0
1
2
3
4
5
TW
oil coal Biomass Nuclear
(U.S. 2004)
1-4¢ 2.3-5.0¢ 6-8¢ 5-7¢
Production cost of energy
6-7¢
25-50¢C
ost,
¢ /kW
-hr
0
5
10
15
20
25
coal Gas oil wind Nuclear Solar
Courtesy of Nate Lewis, Caltech
Storage
Potential of renewable energy sources
Hydro Tides ¤ts
wind Geotherm solar CurrentConsumption
0.1
1
10
100
1000
10000
100000
1000000
TW
SUN: The energy solution ! But how to store it ?
Solar energy:3x1024 joules/year
= 10000 x world populationsupply
(available for billions of years ) !!
Powering the planet with solar fuels
Water electrolysis
SUN: The energy solution ! But how to store it ?
H2
Electricity(batteries)
Water(bio)
photolysis
Solar energy:3x1024 joules/year
= 10000 x world populationsupply
(available for billions of years ) !!
Cracking
(Photo)fermentation
Photobioproduction
Biomass
Powering the planet with solar fuels
Electricity(storage:batteries)
>100000 TW/yr
13 TW/yr20 TW/yr (2030)25 TW/yr (2050) ?
Photovoltaics(reduce the cost 10-fold)
~160,000 km2 of photovoltaic panels can satisfy the énergetic demand in the US (3.3 TW)
SUN: The energy solution ! But how to store it ?
Powering the planet with solar fuels
Solar energy:3x1024 joules/year
= 10000 x world populationsupply
(available for billions of years ) !!
Photobioproduction
Biomass
>100000 TW/yr
100 TW/an
Biofuels
Solar energy:3x1024 joules/year
= 10000 x world populationsupply
(available for billions of years ) !!
13 TW/yr20 TW/yr (2030)25 TW/yr (2050) ?
THE IDEAL CYCLE
FUEL CELLS:Conversion of chemical energy
in electrical energy
2 H2 + O2 2 H2O∆∆∆∆H = - 570 kJ.mol -1
H2 2H+ + 2e-O2 + 4H+ + 4e- 2H2O
H2: 119930 kJ/kg; 33,3 kWh/kg(2.7 fold more than oil; 2.4 fold more than natural gas;5 fold more than coal).
Oudart et al. Inorg. Chem. 2006Eur. J. Inorg. Chem. 2007
Towards Ni-M complexes ….
Photo-productionof hydrogen
M. FONTECAVELaboratoire Chimie et Biologie des Métaux
UMR 5249-CEA/CNRS/UJFGrenoble - France
P.A. JacquesA. Fihri V. Artero
CO2
Pc
P680
Qa
P700
PSIIcytb6
NADPH
O2 + 4 H+
2 H2O
FNR
NADP+
cytf
Cycle de Calvin
[CHO]n
PSILHCLHC LHCLHCPQ(H)2
FdHydrogénase
2 H+H2
RuBP
Calvin cycle
hν
Sacrificial reducing agentOx
e-
M
H+
s
Catalyst
Photosensitizer
H2
Covalent bond
∆rG°= 476 kJ.mol -1
4 photons × 1.23 eV4 electrons involved
∆rG°= 140 kJ.mol -1
1 photon × 1.45 eV 2 electrons involved
1.56 eV ( 800 mn) < Visible radiation < 3.12 eV (400 nm)
Photobiohydrogen and model reaction
N
N
N
N
N
N
Ru
2+
Me-
e-
½ H2
Find the good catalystM
Find the good photosensitizer
Make a multi-functional (supramolecular) system
N
N
N
NN
NRu M
Linker: tunes the electronic communicationbetween the two components
CatalystLight-harvesting
center
Make this reaction useful (sacrificial electron donor: H2O)
H+
NP
PN NiP
P
N
Cy
CyCy
Cy
N
bz
bz bz
bz
Dubois et al. J. Am. Chem. Soc., 2006.
Eher = -0.4V vs Ag/AgCl
Cobaloximes as functional models for hydrogenases. 2. Proton electroreduction catalyzed by difluoroboryl-bis(dimethylglyoximato)-cobalt(II) complexes in organic mediaC. Baffert, V. Artero, M. FontecaveInorg. Chem.. 2007, 46, 1817-1824
Eher = - 0.4 V vs Ag/AgCl in CH3CN92 TON.h-1 (- 0.5 V)pKa= 7,6
NC NH3+NC NH3+
CF3SO3HpKa= 2.6
One of the rare catalyst for H2 oxidationE =-0.27 vs Ag/AgCl
Bio-inspired nanomaterials for Hydrogen evolution: towards alternatives to platinum nanoparticles
Laboratoire de Chimie et Biologie des métauxUMR 5249 CEA/CNRS Université Jospeh Fourier
Laboratoire de Chimie des Surfaces et InterfacesCEA Saclay
H2
Marc FontecaveVincent Artero
Alan Legoff
Serge PalacinBruno Jousselme
e-
Photoelectrochemical cell: water photoelectrolysis
H+
H+
H2
O2
H2O
H+
Photoanode
SC-n : Fe2O3/WO3
Cathode
or
Photocathode
H+
O2 H2
2H2O = O2 + 2H2
NP
PN NiP
P
N
Cy
CyCy
Cy
N
bz
bz bz
bz
Dubois et al. J. Am. Chem. Soc., 2006.
Eher = -0.4V vs Ag/AgCl
Cobaloximes as functional models for hydrogenases. 2. Proton electroreduction catalyzed by difluoroboryl-bis(dimethylglyoximato)-cobalt(II) complexes in organic mediaC. Baffert, V. Artero, M. FontecaveInorg. Chem.. 2007, 46, 1817-1824
Eher = - 0.4 V vs Ag/AgCl in CH3CN92 TON.h-1 (- 0.5 V)pKa= 7,6
NC NH3+NC NH3+
CF3SO3HpKa= 2.6
One of the rare catalysts for H2 oxidationE =-0.27 vs Ag/AgCl
H2/Et3N
Best catalysts:overvoltage, TOF,..
Hydrogenases
Bio-inspired catalystsElectrocatalytic activity demonstrated in solution
What about the electrocatalytic activity of the complexes grafted on the electrodes ???
Bio-inspired nanomaterials for Hydrogen evolution
European patent application EP-08 290 988.8 NOVEL MATERIALS AND THEIR USE FOR THE ELECTROCATALYTIC EVOLUTION OR UPTAKE OF H2
Dubois et al., J. Am. Chem. Soc. 2007,128, 358
N 1s
395400405
Binding energy (eV)
200 Counts/s
RNH2399.9
RNH3+
401.6
MWNTs
ITO
MWNTs electrode functionalizationwith metal catalysts
850860870880890
Binding Energy (eV)
500 Counts/s
2p1/2873.9
2p3/2
856.0Ni
850860870880890
Binding Energy (eV)
500 Counts/s
2p1/2873.9
2p3/2
856.0
850860870880890
Binding Energy (eV)
500 Counts/s
2p1/2873.9
2p3/2
856.0Ni
2p132.2
P
130135
X-ray Photoelectron Spectroscopy (XPS)
- 0.2 V
(Eher= -0.3 V vs Ag/AgCl)
n = 1.5 10-9 mol.cm-2 Scanning Electron Microscopy (SEM)
e-
H+
H2[D
MF
-H]+
-0,8 -0,6 -0,4 -0,2 0,0 0,2
E /V vs Ag/AgCl
2OOµA
European patent application EP-08 290 988.8
CH3CN
Electrocatalytic properties of the modified electrodes
>20.000 turnovers within 1h !! (6 s -1)94% faradaic yieldNo evidence for loss of activity over hours
Controlled potential coulometry(-0.5 V vs Ag/AgCl)CH3CN /[DMFH](OTf) 60 mMGC analysis of H2
n = 1.5 10-9 mol.cm-2
Ni-ITO-MWCNT
DMFH+: pKa=6.1 in CH3CNE°= - 0.1 V vs Ag/AgCl
-0.3 V(overvoltage: 0.2V)
Activity in water !! (N. Guillet, LITEN, CEA)
Ring (Pt)- Disk(vitreous C + Nafion + Ni-NTC) configurationH2SO4 0.1 MRotating-disk electrode measurements
H2 evolution with 18 mV overvoltage
Membrane (Nafion)- Gas Diffusion Layer (Ni-NTC) half-cellH2SO4 0.1 M
A material compatiblewith PEM technology(Nafion membrane,Acidic conditions)
V. ArteroY. OudartA. FihriS. CanaguierA. Legoff
Hydrogen: Water, Sun and CatalystsMarc Fontecave
Laboratoire de Chimie et Biologie des Métaux, Université Joseph Fourier, CNRS, CEA/DSV/iRTSVCEA-Grenoble 17 rue des martyrs 38054 Grenoble cedex 9, France