文献类型：期刊文献

英文题名：Recognition of Surface Oxygen Intermediates on NiFe Oxyhydroxide Oxygen-Evolving Catalysts by Homogeneous Oxidation Reactivity

作者：Hao, Yaming[1,2];Li, Yefei[3];Wu, Jianxiang[1,2];Meng, Lingshen[1,2];Wang, Jinling[4];Jia, Chenglin[1,2];Liu, Tao[1,2];Yang, Xuejing[4];Liu, Zhi-Pan[1,2,3];Gong, Ming[1,2]

机构：[1]Fudan Univ, Dept Chem, Shanghai 200438, Peoples R China;[2]Fudan Univ, Shanghai Key Lab Mol Catalysis & Innovat Mat, Shanghai 200438, Peoples R China;[3]Fudan Univ, Key Lab Computat Phys Sci, Shanghai 200438, Peoples R China;[4]East China Univ Sci & Technol, Natl Engn Lab Ind Wastewater Treatment, Shanghai 200237, Peoples R China

年份：2021

卷号：143

期号：3

起止页码：1493

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20210509846175);WOS:【SCI-EXPANDED(收录号:WOS:000614064400030)】；

基金：M.G. acknowledges supports from the National Key R&D program of China (2019YFC1604602). X.J.Y. acknowledges supports from the National Key Basic Research Program of China (2019YFC1906700) and National Natural Science Foundation of China (21876049, 51878643). Y.F.L. acknowledges supports from National Natural Science Foundation of China (21972023, 21773032). We thank Prof. Harry Gray, Prof. Emily Carter, Prof. Xile Hu, and Dr. John Martirez for the helpful discussion.

语种：英文

外文关键词：Kinetic energy - Reaction intermediates - Atoms - Benzoic acid - Binary alloys - Design for testability - Hydrogen production - Probes - Electrocatalysts - Energy efficiency - Scaffolds

摘要：NiFe oxyhydroxide is one of the most promising oxygen evolution reaction (OER) catalysts for renewable hydrogen production, and deciphering the identity and reactivity of the oxygen intermediates on its surface is a key challenge but is critical to the catalyst design for improving the energy efficiency. Here, we screened and utilized in situ reactive probes that can selectively target specific oxygen intermediates with high rates to investigate the OER intermediates and pathway on NiFe oxyhydroxide. Most importantly, the oxygen atom transfer (OAT) probes (e.g., 4-(diphenylphosphino) benzoic acid) could efficiently inhibit the OER kinetics by scavenging the OER intermediates, exhibiting lower OER currents, larger Tafel slopes, and larger kinetic isotope effect (KIE) values, while probes with other reactivities demonstrated much smaller effects. Combining the OAT reactivity with electrochemical kinetic and operando Raman spectroscopic techniques, we identified a resting Fe=O intermediate in the Ni-O scaffold and a rate-limiting O-O chemical coupling step between a Fe=O moiety and a vicinal bridging O. DFT calculation further revealed a longer Fe=O bond formed on the surface and a large kinetic energy barrier of the O-O chemical coupling step, corroborating the experimental results. These results point to a new direction of liberating lattice O and expediting O-O coupling for optimizing NiFe-based OER electrocatalyst.