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Thermodynamic Oxidation and Reduction Potentials of Photocatalytic Semiconductors in Aqueous Solution
Open accessAbstract
An approach is introduced to calculate the thermodynamic oxidation and reduction potentials of semiconductors in aqueous solution. By combining a newly developed ab initio calculation method for compound formation energy and band alignment with electrochemistry experimental data, this approach can be used to predict the stability of almost any compound semiconductor in aqueous solution. Thirty photocatalytic semiconductors have been studied, and a graph (a simplified Pourbaix diagram) showing their valence/conduction band edges and oxidation/reduction potentials relative to the water redox potentials is produced. On the basis of this graph, the thermodynamic stabilities and trends against the oxidative and reductive photocorrosion for compound semiconductors are analyzed, which shows the following: (i) some metal oxides can be resistant against the oxidation by the photogenerated holes when used as the n-type photoanodes; (ii) all the nonoxide semiconductors are susceptible to oxidation, but they are resistant to the reduction by the photogenerated electrons and thus can be used as the p-type photocathodes if protected from the oxidation; (iii) doping or alloying the metal oxide with less electronegative anions can decrease the band gap but also degrade the stability against oxidation.
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Metadata
- Authors
- Chen, S., & Wang, L.-W.
- Venue
- Chemistry of Materials
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-09-11
- Volume
- 24
- Issue
- 18
- Pages
- 3659-3666
- ISSN
- 0897-4756 (ISSN-L)
- 1520-5002
- OpenAlex
- W2003095845
- Cited by
- 820
- References
- 3
- FWCI
- 11.90
- Type
- journal article
- Language
- en
- Open access
- green
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