Journal
CATALYSIS TODAY
Volume 262, Issue -, Pages 11-23Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.cattod.2015.08.017
Keywords
Artificial photosynthesis; Photoelectrochemistry; Corrosion; Catalysis
Funding
- Office of Science of the U.S. Department of Energy (DOE) [DE-SC0004993]
- Moore Foundation
- Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
- DOE Energy Innovation Hub
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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 CH3OH or CH4. 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. However, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation are unstable, either dissolving or forming insulating surface oxides. We describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO2/Ni and NiOx, 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)). The stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO2 films, along with a discussion of the optical, catalytic, and electronic nature of NiOx films for stabilization of semiconductor photoanodes for water oxidation. (C) 2015 Elsevier B.V. All rights reserved.
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