tailoring nanostructured catalysts in a hydrogen economy prof. paolo fornasiero department of...
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Tailoring Nanostructured Catalysts in a Hydrogen Economy
Prof. Paolo FORNASIERODepartment of ChemistryUniversity of Trieste, Italy
Le filiere dell’energia- Trieste, 26.11.2010
Electrolysis
Reforming
Fermentation+ Reforming
Gasification Pyrolysis
+ Reforming
Biomass
Geothermal
Solar
CarbonOil
Gas
Hydro-electric
Eolic
H2 PRODUCTION TECHNOLOGIESH2 PRODUCTION TECHNOLOGIES
size
of
pro
du
ctio
n
cost
of
avai
lab
le f
eed
sto
cks
size
of
pro
du
ctio
n
cost
of
avai
lab
le f
eed
sto
cks
H2 PRODUCTION & PURIFICATIONH2 PRODUCTION & PURIFICATION
Active and stable catalysts are required for large scale applications
Active and stable catalysts are required for large scale applications
Most efficient catalyst (electrodes) for H2 utilization in Fuel Cells
Most efficient catalyst (electrodes) for H2 utilization in Fuel Cells
Proton Exchange Membrane Fuel Cells
(PEM-FC)
encapsulation of preformed metal nanoparticles into
MOx through different
methodologies
encapsulation of preformed metal nanoparticles into
MOx through different
methodologies
EMBEDDING APPROACHEMBEDDING APPROACH
Rh@Al2O3 FOR METHANE PARTIAL OXIDATION
Rh@Al2O3 FOR METHANE PARTIAL OXIDATION
2H 2 CO 24 O 2
1 CH 2H 2 CO 24 O 2
1 CH
0
20
40
60
80
100
0 50 100 150 200 250
Time (h)
CH
4 c
on
vers
ion
(%
)
Impregnated
Protected
1% Rh impregnated vs 1% Rh embedded @Al1% Rh impregnated vs 1% Rh embedded @Al22OO33
Rh@Al2O3 for MPORh@Al2O3 for MPO
2H 2 CO 24 O 2
1 CH 2H 2 CO 24 O 2
1 CH
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
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
T = 750°CT = 750°C
Ru@LSZ FOR NH3 DECOMPOSITIONRu@LSZ FOR NH3 DECOMPOSITION
3NH 2 22 H 3 N kJ/mol 92 HO298K
Ru@LSZ for NH3 DECOMPOSITIONRu@LSZ for NH3 DECOMPOSITION
B. Lorenzut, T. Montini, C. C. Pavel, M. Comotti, F. Vizza, C. Bianchini and P. Fornasiero, ChemCatChem 2 (2010), 1096-1106 .
GHSVGHSV
4000 mL g-1 h-14000 mL g-1 h-1
30000 mL g-1 h-130000 mL g-1 h-1
Reaction with pure NH3Reaction with pure NH3
T = 500°CT = 500°C
T = 700°CT = 700°C
Cu@TiO2 for PHOTOCATALYTIC H2 PRODUCTION
Cu@TiO2 for PHOTOCATALYTIC H2 PRODUCTION
Cu@TiO2 for PHOTOCATALYTIC H2 PRODUCTIONCu@TiO2 for PHOTOCATALYTIC H2 PRODUCTION
h > 3.0 eVh > 3.0 eV
Water splitting:Very low efficiency
Water splitting:Very low efficiency
Organic molecule as sacrificial agents
Organic molecule as sacrificial agents
Renewable compoundsRenewable compounds
CO2CO2
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), 3916-3925
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), 3916-3925
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 for PHOTOCATALYTIC H2 PRODUCTIONCu@TiO2 for PHOTOCATALYTIC H2 PRODUCTION
0 1 2 3 4 5 60
200
400
600
800
1000
1200
1400
1600
0 10 20 30 40 500
200
400
600
800
1000
1200
1400
1600Ethanol/water 1:1Ethanol/water 1:1 Glycerol 1MGlycerol 1M
Evo
lutio
n ra
te (m
ol/h
)E
volu
tion
rate
(m
ol/h
)
Evo
lutio
n ra
te (m
ol/h
)E
volu
tion
rate
(m
ol/h
)
Time (h)Time (h)
Time (h)Time (h)
Cu@TiO2Cu@TiO2 Cu/TiO2
Cu/TiO2vsvs
H2H2
FE-SEMFE-SEM
OO22 + H + H22OO
atmosphereatmosphere
granular Cugranular Cu22O O
films…films…
……CuO 1D CuO 1D
nanoarchitecturesnanoarchitectures
200 nm
550°C
1 μm
550°C
dry Odry O22
atmospheratmospheree
plane-viewplane-view cross-sectioncross-section
plane-viewplane-view cross-sectioncross-section
H2 p
roduct
ion/L
h-1 m
-2 50
40
30
20
10
00 2 4 6
Cu2O
CuO
time/h
H2 p
roduct
ion/L
h-1 m
-2
0
1
2
3
4
5
0 2 4 6time/h
Cu2O
CuO
Fornasiero P. et al., ChemSusChem 2009, 2, 230
SignificantlySignificantly
betterbetter
performancesperformancesthan commercial Cuthan commercial CuxxO O
(<580 (<580 L hL h-1-1 m m--22 g g--11))
Photocatalytic splitting of HPhotocatalytic splitting of H22O/CHO/CH33OH (1:1) OH (1:1) solutionssolutions
Effect of catalyst Effect of catalyst recyclingrecycling
Radiation switched offRadiation switched offfor 12 h for 12 h
0
5000
10000
15000
20000
25000
30000
0 5 10 15 20 25time / h
high time stabilityof the catalyst
H2 p
roduct
ion/L
h-1 m
-2 g
-1
HH22 production production
UV-Vis (125 W)UV-Vis (125 W)
Vis (125 W)Vis (125 W)
Activity normalized
for the catalyst amount
CuO
DEVELOPMENT OF ADVANCED ELECTRODES FOR SOFCs
DEVELOPMENT OF ADVANCED ELECTRODES FOR SOFCs
Pd-S bondstable
COOH-Ce bondstableCe-OR bond
not stable
CORE-SHELL STRUCTURE DESIGNCORE-SHELL STRUCTURE DESIGN
Pd(1%)@CeO2(9%)/Al2O3
Al2O3
CO oxidation
WGSR Methanol Steam
ReformingJACS 2010, 132, 1402-1409
Pd@CeO2 DISPERSIBLE STRUCTURES AS BUILDING BLOCKS
Pd@CeO2 DISPERSIBLE STRUCTURES AS BUILDING BLOCKS
ZrO2-based solid electrolite 8-YSZ
Cathode:Perovskite ABO3
La1-xSrxNi0.6Fe0.4O3-
Anode:LSCM + CeO2 + Pd
LSCM =La0.8Sr0.2Cr0.5Mn0.5O3
Catalytic componentCeO2-Pd
ADVANCED ELECTRODES for SOFCsADVANCED ELECTRODES for SOFCs
50 μm
50 μm
100 μm
ADVANCED ELECTRODES for SOFCs: ANODEADVANCED ELECTRODES for SOFCs: ANODE
- 15%
- 26%
- 43%
Pd/CeO2-1
Pd/CeO2-2
Pd@CeO2
Maxim
um
pow
er
den
sity
(W
/cm
2)
Time (h)
- 26 %
- 42 %
- 15 %
ADVANCED ELECTRODES for SOFCs: ANODEADVANCED ELECTRODES for SOFCs: ANODE