Boosting the Faradaic Efficiency of Br - -Mediated Photoelectrochemical Epoxidation by Local Acidity on α-Fe 2 O 3 .

Autor: Duan MY; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China., Tang DJ; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China., Yang J; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China., Yang SP; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China., Deng CY; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China., Zhao YK; Department of Chemistry, National University of Singapore, 12 Science Drive 2, Singapore, 117549, Singapore., Li JK; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China., Zhang YC; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China., Chen CC; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China., Zhao JC; Key Laboratory of Photochemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.; University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Jazyk: angličtina
Zdroj: Advanced science (Weinheim, Baden-Wurttemberg, Germany) [Adv Sci (Weinh)] 2024 Jul; Vol. 11 (25), pp. e2401685. Date of Electronic Publication: 2024 Apr 25.
DOI: 10.1002/advs.202401685
Abstrakt: The redox mediated photoelectrochemical (PEC) or electrochemical (EC) alkene oxidation process is a promising method to produce high value-added epoxides. However, due to the competitive reaction of water oxidation and overoxidation of the mediator, the utilization of the electricity is far below the ideal value, where the loss of epoxidation's faradaic efficiency (FE) is ≈50%. In this study, a Br - /HOBr-mediated method is developed to achieve a near-quantitative selectivity and ≈100% FE of styrene oxide on α-Fe 2 O 3 , in which low concentration of Br - as mediator and locally generated acidic micro-environment work together to produce the higher active HOBr species. A variety of styrene derivatives are investigated with satisfied epoxidation performance. Based on the analysis of local pH-dependent epoxidation FE and products distribution, the study further verified that HOBr serves as the true active mediator to generate the bromohydrin intermediate. It is believed that this strategy can greatly overcome the limitation of epoxidation FE to enable future industrial applications.
(© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)
Databáze: MEDLINE
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