Abstract
Metal oxide semiconductor-based photo(electro)catalysis has drawn increasing attention due to its prominent applications in solar energy conversion and environmental remediation. The photogenerated valence-band hole and conduction-band electron diffuse to the metal oxide/solution interface and trigger subsequent chemical conversions involving multiple proton-coupled electron (hole) transfer (PCET) steps to reconstruct chemical bonds. We review herein our recent work on regulating such PCET processes in photocatalytic oxygen reduction and water oxidation. The reaction thermodynamics, kinetics, and PCET pathways can be tuned by controlling the crystal facet and surface structure. Reductive conversion of organic halides by PCET on pristine or modified TiO2 as well as its unique kinetic features are also discussed. Such mechanistic fundamentals of interfacial reactions could guide development of photocatalysts with improved efficiency and desired selectivity.
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Acknowledgements
The authors are grateful for financial support of this work from the 973 Project (no. 2013CB632405), National Natural Science Foundation of China (NSFC, nos. 21407153, 21537003, 21590811, and 21521062) and “Strategic Priority Research Program” of the Chinese Academy of Sciences (no. XDA09030200).
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Special Issue of the 1st International Symposium on Photocatalysis at Fuzhou University.
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Zhu, Q., Duan, R., Ji, H. et al. Interfacial proton-coupled electron transfer in metal oxide semiconductor photocatalysis. Res Chem Intermed 43, 4997–5009 (2017). https://doi.org/10.1007/s11164-017-3043-z
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DOI: https://doi.org/10.1007/s11164-017-3043-z