Zinc-indium-sulfide favors efficient C − H bond activation by concerted proton-coupled electron transfer

Xuejiao Wu (), Xueting Fan, Shunji Xie, Ivan Scodeller, Xiaojian Wen, Dario Vangestel, Jun Cheng () and Bert Sels ()
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Xuejiao Wu: KU Leuven
Xueting Fan: Xiamen University
Shunji Xie: Xiamen University
Ivan Scodeller: KU Leuven
Xiaojian Wen: Xiamen University
Dario Vangestel: KU Leuven
Jun Cheng: Xiamen University
Bert Sels: KU Leuven

Nature Communications, 2024, vol. 15, issue 1, 1-11

Abstract: Abstract C − H bond activation is a ubiquitous reaction that remains a major challenge in chemistry. Although semiconductor-based photocatalysis is promising, the C − H bond activation mechanism remains elusive. Herein, we report value-added coupling products from a wide variety of biomass and fossil-derived reagents, formed via C − H bond activation over zinc-indium-sulfides (Zn-In-S). Contrary to the commonly accepted stepwise electron-proton transfer pathway (PE-ET) for semiconductors, our experimental and theoretical studies evidence a concerted proton-coupled electron transfer (CPET) pathway. A pioneering microkinetic study, considering the relevant elementary steps of the surface chemistry, reveals a faster C − H activation with Zn-In-S because of circumventing formation of a charged radical, as it happens in PE-ET where it retards the catalysis due to strong site adsorption. For CPET over Zn-In-S, H abstraction, forming a neutral radical, is rate-limiting, but having lower energy barriers than that of PE-ET. The rate expressions derived from the microkinetics provide guidelines to rationally design semiconductor catalysis, e.g., for C − H activation, that is based on the CPET mechanism.

Date: 2024
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DOI: 10.1038/s41467-024-49265-2

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