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Tailoring Nanostructured Catalysts in a Hydrogen Economy
Prof. Paolo FORNASIERO Department of Chemistry University of Trieste, Italy Le filiere dell’energia- Trieste,
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cost of available feedstocks size of production
H2 PRODUCTION TECHNOLOGIES Eolic Electrolysis Hydro- electric Reforming Solar Geothermal cost of available feedstocks size of production Fermentation + Reforming Biomass Gasification Pyrolysis + Reforming Gas Oil Carbon
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Proton Exchange Membrane Fuel Cells (PEM-FC)
H2 PRODUCTION & PURIFICATION O2 H2 H2O Proton Exchange Membrane Fuel Cells (PEM-FC) Active and stable catalysts are required for large scale applications Most efficient catalyst (electrodes) for H2 utilization in Fuel Cells
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EMBEDDING APPROACH encapsulation of preformed metal nanoparticles into MOx through different methodologies
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Rh@Al2O3 FOR METHANE PARTIAL OXIDATION
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1% Rh impregnated vs 1% Rh embedded @Al2O3
for MPO 1% Rh impregnated vs 1% Rh T = 750°C Protected Impregnated T. Montini, A. M. Condó, N. Hickey, F. Lovey, L. De Rogatis, P. Fornasiero and M. Graziani, Applied Catalysis B: Environmental 73 (2007) 84-97
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Ru@LSZ FOR NH3 DECOMPOSITION
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Ru@LSZ for NH3 DECOMPOSITION
Reaction with pure NH3 GHSV T = 500°C 4000 mL g-1 h-1 T = 700°C 30000 mL g-1 h-1 B. Lorenzut, T. Montini, C. C. Pavel, M. Comotti, F. Vizza, C. Bianchini and P. Fornasiero, ChemCatChem 2 (2010),
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Cu@TiO2 for PHOTOCATALYTIC H2 PRODUCTION
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Organic molecule as sacrificial agents
for PHOTOCATALYTIC H2 PRODUCTION hn > 3.0 eV Water splitting: Very low efficiency Organic molecule as sacrificial agents Renewable compounds
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Cu@TiO2 for PHOTOCATALYTIC H2 PRODUCTION
Experimental condition: Medium pressure Hg lamp 125W 0.500 g catalyst 240 mL of solution Argon flow 15 mL/min Ar in Ar in Ar out Cu/TiO2 vs Ethanol/water 1:1 Glycerol 1M Evolution rate (mmol/h) Evolution rate (mmol/h) H2 CO2 Time (h) Time (h) V. Gombac, L. Sordelli, T. Montini, J. J. Delgado, A. Adamski, G. Adami, M. Cargnello, S. Bernal and P. Fornasiero, Journal of Physical Chemistry A 114 (2010),
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…CuO 1D nanoarchitectures
plane-view cross-section FE-SEM O2 + H2O atmosphere granular Cu2O films… plane-view cross-section 200 nm 550°C 1 μm dry O2 atmosphere …CuO 1D nanoarchitectures
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Photocatalytic splitting of H2O/CH3OH (1:1) solutions
H2 production Fornasiero P. et al., ChemSusChem 2009, 2, 230 Effect of catalyst recycling Radiation switched off for 12 h 5000 10000 15000 20000 25000 30000 5 10 15 20 25 time / h high time stability of the catalyst H2 production/L h-1 m-2 g-1 UV-Vis (125 W) H2 production/L h-1 m-2 50 40 30 20 10 2 4 6 Cu2O CuO time/h Activity normalized for the catalyst amount CuO Vis (125 W) H2 production/L h-1 m-2 1 2 3 4 5 6 time/h Cu2O CuO Significantly better performances than commercial CuxO (<580 L h-1 m-2 g-1) 13
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DEVELOPMENT OF ADVANCED ELECTRODES FOR SOFCs
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CORE-SHELL STRUCTURE DESIGN
COOH-Ce bond stable Ce-OR bond not stable Pd-S bond stable
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Methanol Steam Reforming
DISPERSIBLE STRUCTURES AS BUILDING BLOCKS Al2O3 CO oxidation WGSR Methanol Steam Reforming JACS 2010, 132,
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ZrO2-based solid electrolite
ADVANCED ELECTRODES for SOFCs Cathode: Perovskite ABO3 La1-xSrxNi0.6Fe0.4O3-d ZrO2-based solid electrolite 8-YSZ Anode: LSCM + CeO2 + Pd LSCM =La0.8Sr0.2Cr0.5Mn0.5O3 Catalytic component CeO2-Pd
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ADVANCED ELECTRODES for SOFCs: ANODE
50 μm 100 μm
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Maximum power density (W/cm2)
ADVANCED ELECTRODES for SOFCs: ANODE - 15 % - 15% Maximum power density (W/cm2) - 26% - 26 % Pd/CeO2-1 - 42 % Pd/CeO2-2 - 43% Time (h)
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