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Zinc-indium-sulfide favors efficient C - H bond activation by concerted proton-coupled electron transfer.
Wu, Xuejiao; Fan, Xueting; Xie, Shunji; Scodeller, Ivan; Wen, Xiaojian; Vangestel, Dario; Cheng, Jun; Sels, Bert.
Affiliation
  • Wu X; Center for Sustainable Catalysis and Engineering, Faculty of Bioscience Engineering, KU Leuven, Heverlee, 3001, Belgium. xuejiao.wu@kuleuven.be.
  • Fan X; College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
  • Xie S; College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
  • Scodeller I; Center for Sustainable Catalysis and Engineering, Faculty of Bioscience Engineering, KU Leuven, Heverlee, 3001, Belgium.
  • Wen X; College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
  • Vangestel D; Center for Sustainable Catalysis and Engineering, Faculty of Bioscience Engineering, KU Leuven, Heverlee, 3001, Belgium.
  • Cheng J; College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China. chengjun@xmu.edu.cn.
  • Sels B; Center for Sustainable Catalysis and Engineering, Faculty of Bioscience Engineering, KU Leuven, Heverlee, 3001, Belgium. bert.sels@kuleuven.be.
Nat Commun ; 15(1): 4967, 2024 Jun 11.
Article in En | MEDLINE | ID: mdl-38862582
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.

Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: Nat Commun Journal subject: BIOLOGIA / CIENCIA Year: 2024 Document type: Article Affiliation country: Country of publication:

Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: Nat Commun Journal subject: BIOLOGIA / CIENCIA Year: 2024 Document type: Article Affiliation country: Country of publication: