Materials and Mechanisms in Solar Hydrogen Production
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1 Materials and Mechanisms in Solar Hydrogen Production CO 2 + H 2 O Jan Philipp Hofmann Emiel Hensen
2 Photoelectrochemistry Crucial parameters: Bandgap Lifetime of charge carriers Concentration of the defects Charge carriers free path Stability against photocorrosion Interface properties Requirements: solar to H 2 efficiency > 10 % lifetime > 10 years
3 Materials choice: band gaps and band positions E 0 vs NHE / V H + /H 2 H 2 O/O 2 GaP 2.25 ev GaAs 1.4 ev TiO ev 388 nm ZnO 3.2 ev Fe 2 O ev 590 nm 517 nm Cu 2 O 2.1 ev WO ev SnO ev ZnS 3.7 ev 335 nm FeS ev CdSe 1.7 ev CdS 2.4 ev / Inorganic Materials Chemistry PAGE 2
4 Anton Litke, PhD Bjorn Joos, MSc Materials for light harvesting making use of faults: twinned Cd 0.5 Zn 0.5 S no additives 0.1M NaOH 0.1M EN 0.1M KCl / degree H 2 production / mmol g -1 h -1 H 2 production / mmol g -1 h optimized loading: 5.7 mg in 50 ml no co-cat. 1wt% Pt 1wt% NiS 2.3 loading 50 mg in 50 ml no add. 0.1M NaOH 0.1M EN 0.1M KCl twinning in pyrite FeS 2 zinc blende structure PAGE 3
5 Twinned Cd 0.5 Zn 0.5 S: Enhanced charge carrier separation CB E, ev H 2 H + /H 2 H + S 2 2- S 2 2- /S 2- S 2- VB M. Liu et al., Nature Communications, 2013, 4, HR-TEM + TEM hologram of Cd 0.5 Zn 0.5 S courtesy of T. Niermann, TU Berlin / Inorganic Materials Chemistry PAGE 4
6 Probing reactions on photocatalysts Combined IR and UV-Vis Spectroscopy Anton Litke, PhD IR probe reactions at surface of nanoparticles UV-Vis probe photoluminescence UV-Vis probe absorption target time resolution s / Inorganic Materials Chemistry PAGE 5
7 Interfaces: Theory of water oxidation e.g. Au/TiO 2 & CoO/TiO 2 Bartek Szyja, PD Mechanism: 2 H 2 O 4 H e + O 2 Au 4 /TiO 2 Co 4 O x /TiO 2 / Inorganic Materials Chemistry PAGE 6
8 Cu 2 O as photoabsorber Quanbao Ma, PD Andrey Goryachev, PhD Elif Teksen, BSc Earth-abundant materials production by chemical bath deposition or hydrothermal reaction ph dependent preferential growth in chemical bath PAGE 7
9 Cu 2 O as photoabsorber stability Cu 2 O before photoelectrochemical reaction Cu 2 O after photoelectrochemical reaction / Inorganic Materials Chemistry PAGE 8
10 Protection Multilayer model systems co-catalyst Paracchino et al., Nat. Mater., 10, 2011, 456. R,C (PL) R, C (Abs) layer model of photoelectrode with resistances and capacitances of layers (left) and interfaces (right) Protective layer (PL) Cu 2 O (Absorber) FTO glass R (PL CoCat) R (Abs PL) / Inorganic Materials Chemistry PAGE 9
![of XPS peaks [1] Inorganic Materials Group/Solar Fuels Catalysis](/docs-images/72/67900793/images/11-2.jpg "[1] U.K. Demirok, et al., J. Phys. Chem.")
11 Quanbao Ma, PD Andrey Goryachev, PhD Charge carrier dynamics probed by photoelectron spectroscopy bias voltage dependent shift of XPS peaks [1] Inorganic Materials Group/Solar Fuels Catalysis [1] U.K. Demirok, et al., J. Phys. Chem. B, 108 (2004) PAGE 10
12 Interfaces: Dynamic XPS Dynamic XPS = analogue of electric impedance spectroscopy + no electrolyte surface science (vacuum) technique + not destructive no photocorrosion + surface sensitive non bulk analysis + chemically specific element specific analysis of electronic behavior R C Data: (Ertas, Demirok, Atalar, & Suzer, 2005; Suzer, Sezen, Ertas, & Dâna, 2010) / Inorganic Materials Chemistry PAGE 11
13 Suggestion for Goals, challenges and roadmap Stable Solar Fuels device with >15% overall efficiency 1. Novel light harvesting materials with high quantum h 2. Efficient co-catalysts 3. Earth-abundant materials 4. Device integration (high-tech system) 5. Integration into current energy infrastructure Highly multidisciplinary efforts needed Chemistry, Physics, Engineering / Inorganic Materials Chemistry PAGE 12
14 The Solar Fuels Scientist recently seen in Eindhoven / Inorganic Materials Chemistry found at: bsrobo.wikispaces.com PAGE 13
15 Nederlands Instituut voor Onderzoek in de Katalyse Solar Fuels Catalysis Graduate programme started in September 2013 Highly interdisciplinary Master and PhD programmes Focus on all aspects of Solar Energy Conversion into Clean Fuels Utrecht University (UU) In-situ Spectroscopy of Catalyst Materials Technical University Eindhoven (TU/e) Catalyst Materials and Mechanisms Leiden University (UL) Electrochemistry / Electrocatalysis Twente University (UT) - Photocatalysis
16 Solar Fuels Catalysis Graduate Programme Prepare the students for a career in science by offering them the best possible training and education in the challenging research field of catalytic conversion of sun light, carbon dioxide and water into fuels 15
17 Thanks for your attention! / Inorganic Materials Chemistry found at: bsrobo.wikispaces.com PAGE 16
18 / Inorganic Materials Chemistry PAGE 17
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