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Optimizing the semiconductor–metal-single-atom interaction for photocatalytic reactivity

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Abstract

Metal single-atom (MSA) catalysts with 100% metal atom utilization and unique electronic properties are attractive cocatalysts for efficient photocatalysis when coupled with semiconductors. Owing to the absence of a metal–metal bond, MSA sites are exclusively coordinated with the semiconductor photocatalyst, featuring a chemical-bond-driven tunable interaction between the semiconductor and the metal single atom. This semiconductor–MSA interaction is a platform that can facilitate the separation/transfer of photogenerated charge carriers and promote the subsequent catalytic reactions. In this Review, we first introduce the fundamental physicochemistry related to the semiconductor–MSA interaction. We highlight the ligand effect on the electronic structures, catalytic properties and functional mechanisms of the MSA cocatalyst through the semiconductor–MSA interaction. Then, we categorize the state-of-the-art experimental and theoretical strategies for the construction of the efficient semiconductor–MSA interaction at the atomic scale for a wide range of photocatalytic reactions. The examples described include photocatalytic water splitting, CO2 reduction and organic synthesis. We end by outlining strategies on how to further advance the semiconductor–MSA interaction for complex photocatalytic reactions involving multiple elementary steps. We provide atomic and electronic-scale insights into the working mechanisms of the semiconductor–MSA interaction and guidance for the design of high-performance semiconductor–MSA interface photocatalytic systems.

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Fig. 1: Fundamental physicochemistry of the semiconductor–MSA interaction.
Fig. 2: Development history of the semiconductor–MSA interaction.
Fig. 3: Construction of the semiconductor–MSA architecture.
Fig. 4: Identification of the semiconductor–MSA interaction.
Fig. 5: Charge separation/transfer and surface catalytic dynamics.
Fig. 6: Tuning the semiconductor–MSA interaction for water splitting.
Fig. 7: Tuning the semiconductor–MSA interaction for CO2 reduction.
Fig. 8: Tuning the semiconductor–MSA interaction for organic synthesis.
Fig. 9: Strategies for constructing an advanced semiconductor–MSA architecture.

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Acknowledgements

The authors are grateful for the financial support of this work from the National Natural Science Fund for Distinguished Young Scholars (grant 52025133), the Tencent Foundation through the XPLORER PRIZE, the Beijing Natural Science Foundation (grant Z220020), the National Natural Science Foundation of China (grant 22002003) and the Fund of the State Key Laboratory of Solidification Processing in NWPU (grant SKLSP202004).

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Zhou, P., Luo, M. & Guo, S. Optimizing the semiconductor–metal-single-atom interaction for photocatalytic reactivity. Nat Rev Chem 6, 823–838 (2022). https://doi.org/10.1038/s41570-022-00434-1

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