1. Zinc-indium-sulfide favors efficient C − H bond activation by concerted proton-coupled electron transfer.
- Author
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Wu, Xuejiao, Fan, Xueting, Xie, Shunji, Scodeller, Ivan, Wen, Xiaojian, Vangestel, Dario, Cheng, Jun, and Sels, Bert
- Subjects
CHARGE exchange ,PROTON transfer reactions ,SEMICONDUCTOR design ,SURFACE chemistry ,ACTIVATION energy ,RADICALS (Chemistry) - 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. The knowledge of semiconductor photocatalysis in C − H bond activation remains limited. Here, the authors report comprehensive mechanistic studies to unveil the semiconductor-rare concerted proton-coupled electron transfer mechanism for C − H bond activation over Zn-In-S. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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