Operando Analyses of Solar Fuels Light Absorbers and Catalysts

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• 作者：Hans-Joachim Lewerenz^a ; ^b ; ^{lewerenz@caltech.edu" class="auth_mail" title="E-mail the corresponding author} ; Michael F. Lichterman^a ; ^c ; ^{mLichter@caltech.edu" class="auth_mail" title="E-mail the corresponding author} ; Matthias H. Richter^a ; ^c ; ; Ethan J. Crumlin^d ; Shu Hu^a ; ^c ; Stephanus Axnanda^d ; Marco Favaro^d ; ^e ; ^f ; Walter Drisdell^e ; ^f ; Zahid Hussain^d ; Bruce S. Brunschwig^g ; Zhi Liu^d ; ^h ; ⁱ ; Anders Nilsson^j ; Alexis T. Bell^f ; ^k ; Nathan S. Lewis^a ; ^c ; ^g ; ^{nslewis@caltech.edu" class="auth_mail" title="E-mail the corresponding author} ; Daniel Friebel^j
• 关键词：Catalysis ; Semiconductors ; Protection ; operando spectroscopy ; artificial photosynthesis
• 刊名：Electrochimica Acta
• 出版年：2016
• 出版时间：1 September 2016
• 年：2016
• 卷：211
• 期：Complete
• 页码：711-719
• 全文大小：2080 K

文摘

Operando synchrotron radiation photoelectron spectroscopy in the tender X-ray energy range has been used to obtain information on the energy-band relations of semiconductor and metal-covered semiconductor surfaces while in direct contact with aqueous electrolytes under potentiostatic control. The system that was investigated consists of highly doped Si substrates that were conformally coated with ∼70 nm titania films produced by atomic-layer deposition. TiO₂/electrolyte and Si/TiO₂/Ni/electrolyte interfaces were then analyzed by synchrotron radiation photoelectron spectroscopy. The PES data allows for determination of the flat-band position and identification of potential regions in which Fermi level pinning, depletion, or accumulation occurred. Operando X-ray absorption spectroscopy (XAS) techniques were additionally used to investigate the properties of heterogeneous electrocatalysts for the oxygen-evolution reaction. Operando XAS including the pre-edge, edge and EXAFS regions allowed the development of a detailed picture of the catalysts under operating conditions, and elucidated the changes in the physical and electronic structure of the catalyst that accompanied increases in the applied potential. Specifically, XAS data, combined with DFT studies, indicated that the activity of the electrocatalyst correlated with the formation of Fe dopant sites in γ-NiOOH.