Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

Lichterman, Michael F.; Sun, Ke; Hu, Shu; Zhou, Xinghao; McDowell, Matthew T.; Shaner, Matthew R.; Richter, Matthias H.; Crumlin, Ethan J.; Carim, Azhar I.; Saadi, Fadl H.; Brunschwig, Bruce S.; Lewis, Nathan S.

doi:10.1016/j.cattod.2015.08.017

Title: Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

Journal Article · Sun Oct 25 00:00:00 EDT 2015 · Catalysis Today

DOI: https://doi.org/10.1016/j.cattod.2015.08.017 · OSTI ID:1379158

Lichterman, Michael F. ^[1]; Sun, Ke ^[1]; Hu, Shu ^[2]; Zhou, Xinghao ^[3]; McDowell, Matthew T. ^[1]; Shaner, Matthew R. ^[1]; Richter, Matthias H. ^[3]; Crumlin, Ethan J. ^[4]; Carim, Azhar I. ^[5]; Saadi, Fadl H. ^[3]; Brunschwig, Bruce S. ^[4]; Lewis, Nathan S. ^[6]

California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering, Joint Center for Artificial Photosynthesis
California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering, Joint Center for Artificial Photosynthesis, Beckman Inst.
California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering, Joint Center for Artificial Photosynthesis, Beckman Inst., Kavli Nanoscience Inst.

Small-band-gap (E _g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H ₂ (g) or a reduced-carbon species such as CH₃ OH or CH ₄. To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O ₂ (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. But, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation are unstable, either dissolving or forming insulating surface oxides. Here, we describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO ₂ /Ni and NiO _x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for > 100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). Furthermore, the stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO ₂ films, along with a discussion of the optical, catalytic, and electronic nature of NiO _x films for stabilization of semiconductor photoanodes for water oxidation.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; SC0004993

OSTI ID:: 1379158

Journal Information:: Catalysis Today, Journal Name: Catalysis Today Journal Issue: C Vol. 262; ISSN 0920-5861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
artificial photosynthesis
catalysis
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Title: Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

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