Abstract
Photocatalysis has emerged as a green protocol for biorefineries thanks to sustainable energy input. The unique radical mechanism of photocatalysis allows the decomposition of raw biomass and the precise functionalization of platform molecules, but radicals with open-shell electronic structures are highly active, resulting in diverse products. Control of the radical mechanism relies on photocatalysts guiding interfacial charge transfer for chemical bond breaking. The reaction behaviour of radicals and the surface states of semiconductor photocatalysts are therefore crucial for controlling the efficiency and selectivity of biorefineries. Here we discuss the factors that influence the interfacial charge transfer and radical reactions in photocatalytic biorefineries, including the surface structure and electronic states of semiconductors and the catalytic properties of cocatalysts. Recognition of these factors will feed back the expected structure of semiconductors and cocatalysts, assisting with the design of photocatalysts for the efficient and selective refining of native biomass.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (22025206, 22172157, 22202199 and 21991090), the Dalian Innovation Support Plan for High Level Talents (2022RG13), DICP (grant no. DICP I202326) and the Youth Innovation Promotion Association (YIPA) of the Chinese Academy of Sciences (2023192). We also acknowledge instrumental support from the Liaoning Key Laboratory of Biomass Conversion for Energy and Material. Y. Zou is acknowledged for drawing the Graphical Abstract.
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F.W. and N.L. conceived the outline of this Review. Z.G., P.R. and N.L. composed the figures, and wrote and revised the manuscript. L.S. collected and organized the references.
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Gao, Z., Ren, P., Sun, L. et al. Photocatalysts for steering charge transfer and radical reactions in biorefineries. Nat. Synth 3, 438–451 (2024). https://doi.org/10.1038/s44160-024-00499-4
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DOI: https://doi.org/10.1038/s44160-024-00499-4