Vincent Artero, CEA/Life Science Division, Grenoble, France .... x structures and
pyridinic rings are keys for a high (4e-) ORR activity in acidic media.
EnzHyd Enzymes and organometallic catalysts in hydrogen fuel cells PAN-H 2008
Vincent Artero iRTSV/CBM CEA Grenoble
The EnzHyd project Title: Enzymes and organometallic catalysts in hydrogen fuel cells Partners: CEA/DSV/IBS: hydrogenase enzymes CEA/DSV/iRTSV/LCBM: hydrogenase mimics CEA/DSM/IRAMIS/SPEC: hydrogenase/CNT hybrid CEA/DSM/IRAMIS/SPCSI: Noble-metal free O2-reducing materials CEA/DRT/LITEN/DTNM/LCI: integration in H2-Fuel-cells
Starting date : 01/01/2008 End: 31/12/2011 Total cost : 1 774 k€ ANR funding : 818 k€
Vincent Artero, CEA/Life Science Division, Grenoble, France
Context and challenges
Limited platinum stocks :
Gordon et al. PNAS 2006
Total Pt mining 200 tonnes/year 0.4 g Pt/kW in H2 fuel-cells (2010) → 30 gPt per vehicle (75 kW) = 22% of its price! 75 years required to equip all 500 millions vehicles on the Earth (30% of total Pt on the Earth) With a Pt recycling score of 50%, total stocks will then be exhausted within 15 ans Such a model is economically viable and sustainable only if the Pt load is reduced by a factor 10 Vincent Artero, CEA/Life Science Division, Grenoble, France
Objectives and positionning CYTOCHROME C OXIDASE 4-electron reduction of O2 to water Limited overpotential requirement
HYDROGENASES Bidirectional catalysis No overpotential requirement Vincent Artero, CEA/Life Science Division, Grenoble, France
Scientific and technological barriers - Incorporating hydrogenase enzymes as anode catalysts of a H2 fuel-cell - Implementing bioinspired mimics of the active site of hydrogenase in a H2 fuel-cell anode
- Developing new noble-metal free cathode catalysts for O2 reduction - Demonstration that an operational PEM H2fuel cell without noble metal can be assembled.
Vincent Artero, CEA/Life Science Division, Grenoble, France
Grafting hydrogenases onto carbon nanotubes Hydrogenase D. desulfuricans [FeFe] D. baculatum [NiFeSe]
Aqueous gel loaded with CNT-Hydrogenase
37w% H2ase (XPS)
N2 +
Pristine CNTs
CNTs-H2ase
1µm
1µm
H2
Electrochemical tests on 1cm2 carbon grid with nafion membrane
Current (µA)
20 10
N2
0 E (V vs Ag/AgCl)
-10 -0,2
Vincent Artero, CEA/Life Science Division, Grenoble, France
0
0,2
0,4
From hydrogenases to catalytic nanomaterials half-cell conf.
135°C 4MPa
solution Nafion NRE212 NRE 212 CS Nafion CSmembrane membrane
Catalytic material deposited on a Gas diffusion layer (BASF LT 1200W) and deposited c Gas Diffusion Layer (BASF LT1200W) 14 mm
N H22 N2 + H2
H2 N2 -0,4 blank
-0,2
0
0,2
0,4
1 mA.cm–2
200 nm
0,6
Bidirectional catalysis No overpotential requirement Outsanding stability in H2SO4 0.5M
Potential (E) / V European patent application EP-08 290 988.8 Le Goff et al., Science 2009
Vincent Artero, CEA/Life Science Division, Grenoble, France
CO-tolerant material
-2
Normalized current density /mA.cm .mg
-1
300 250 200
1 atm. H2 + 50 ppm CO Surface catalyst concentration: 2±0.5 10−9 mol. cm−2
150
Hydrogen oxidation at 0.25 V vs NHE 100 commercial MEA (0.5 mgPt.cm-2)
50 0 0
20
40 60 Time /mn
80
100
Tran et al. Angew. Chem. Int. Ed. 2011 Vincent Artero, CEA/Life Science Division, Grenoble, France
Metal-macrocycles and carbon nanotubes for alkaline O2 reduction
Oxidised MWCNTs > b-MWCNTs > SWCNTs > DWCNTs. Iron phthalocyanine/CNTs catalysts show the best ORR performance in alkaline electrolyte and require only 60 mV more overpotential than Pt/C reference material. Morozan et al. Carbon 2011 Vincent Artero, CEA/Life Science Division, Grenoble, France
Pyrolyzed Co/benzotriazole/CNT for acidic O2 reduction
After pyrolysis, both Co–Nx structures and pyridinic rings are keys for a high (4e-) ORR activity in acidic media. This material requires only 200 mV more overpotential than Pt/C reference material Morozan et al. ChemSusChem 2012 Morozan et al. Phys. Chem. Chem. Phys., 2011 Vincent Artero, CEA/Life Science Division, Grenoble, France
The first noble metal-free PEMFC Passive planar open-end fuel-cell using atmospheric O2 and H2
Successful demonstration that an operational PEM H2-fuel cell (23 µW.cm-2) without noble metal can be assembled.
Vincent Artero, CEA/Life Science Division, Grenoble, France
Conclusions & perspectives - O2-tolerant hydrogenases incorporated into enzyme/CNT electrocatalytic materials
- Bioinspired mimics of the active site of hydrogenase implemented in a H2 fuel-cell anode - New noble-metal free cathode catalysts for O2 reduction developped - Successful demonstration that an operational PEM H2-fuel cell ( 23 µW.cm-2) without noble metal can be assembled. - Optimization of the materials and deposition processes is still required
Vincent Artero, CEA/Life Science Division, Grenoble, France
Valorisation • Publications: 1. A. Le Goff et al., Science 2009, 326, 1384. 2. P. D. Tran et al. Energy Environ. Sci., 2010, 3, 727-737. 3. A. Morozan, et al., Energy Environ. Sci., 2011, 4, 1238-1254. 4. A. Morozan et al., Phys. Chem. Chem. Phys., 2011, 13, 21600-21607. 5. A. Morozan et al., Carbon, 2011, 49, 4839-4847. 6. A. Morozan et al., Energy Environ. Sci., 2011, 4, 1238-1254. 7. P. D. Tran et al., Angew. Chem., Int. Ed., 2011, 50, 1371-1374. 8. A. Morozan et al. ChemSusChem., 2012, sous presse. 9. A. Morozan et al., Chem. Comm. soumis. 10. A Noble-Metal Free PEMFC Hydrogen Fuel-Cell, in preparation 11. Artero et al. Pour la science 2011
•Patent deposit: Method for preparing metal-free nitrogen-containing carbon nanotubes, A. Morozan, B. Jousselme, Demande BD12879 •Communications 21 invited talks in international conférences (Gordon research conferencesACS-meeting, US-DOE meeting…) 11 invited talks in foreign research institutes 20 talks at national and local meetings
Vincent Artero, CEA/Life Science Division, Grenoble, France
