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Equilibrium-Reduction of Ceria-based Materials for Solar Fuel ProductionFriedemann Call1, Martin Roeb1, Christian Sattler1, Martin Schmücker2, Brendan Bulfin3, Igor Shvets3
1Institute of Solar Research (DLR) ²Institute of Material Research (DLR)
³School of Physics, Trinity College Dublin
www.DLR.de • Chart 1 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
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Institute of Solar Research
-Evaluation Renewable Energies – 26th January 2009
-Prof. Dr. Robert Pitz-Paal – p 2
www.DLR.de • Chart 2 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
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Thermochemical Redox Cycles for Synthesis Gas
www.DLR.de • Chart 3 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
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The Bottle Neck: The Redox Material
www.DLR.de • Chart 4 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
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Doping Results
www.DLR.de • Chart 5 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
F. Call et al., The American Journal of Analytical Chemistry, Vol. 117, No. 46, pp. 24129–24137, 2013.
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Reduction in Equilibrium
www.DLR.de • Chart 6 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
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Results in Equilibirum
www.DLR.de • Chart 7 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
F. Call et al., Journal of Physical Chemistry C, under revision
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Feeding a Physical Reaction Model
www.DLR.de • Chart 8 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
[Bul 13] B. Bulfin et al. The Journal of Physical Chemistry C, Vol. 117, No. 46, pp. 24129–24137, 2013.
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Feeding a Physical Reaction Model
www.DLR.de • Chart 9 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
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Ellingham Diagrams of Doped-Materials
www.DLR.de • Chart 10 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
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Basic Efficiency Calculations
www.DLR.de • Chart 11 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
F. Call et al., PhD Thesis. Will be submitted next month.
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DLR.de • Folie 12 > Wettbewerb der Visionen > Dünger für die Welt > Friedemann Call, Jan Felinks und Matthias Lange > 27.10.2014
Haber‐Bosch ProcessNH3
H HO
H H
CeO2‐x
O
‐1100°C ‐1400°C
H2from water
CuOx
N N
O O
O O
‐880°C ‐840°C
N2from air
New Idea: Ammonia Production
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Conclusions
- Ceria-based materials are the most promising materials for Solar Fuels- Doping yields significant improvements
- Data of equilibrium measurements (varying T and p(O2)) can feed physical reaction model yielding a δ(T, p(O2))-function that can be used to construct Ellingham diagrams (reduction enthalpy and entropy)
www.DLR.de • Chart 13 > Thermochemical Solar Fuel Production > Friedemann Call > 10.12.2014
Thank you for your attention!
TGA
, O, O-function
reaction model Ellingham-function
∆∆
- New idea: Using a combined thermochemical cycle to produce H2 and N2, the precursor for Ammonia