文献类型：期刊文献

英文题名：The Identity of Nickel Peroxide as a Nickel Superoxyhydroxide for Enhanced Electrocatalysis

作者：Yang, Yizhou[1];Li, Jili[2,3];Li, Chong[1];Gong, Ming[2,3];Wang, Xue[1];Yang, Xuejing[1];Wang, Hualin[1];Li, Ye-Fei[2,3,4];Liu, Zhi-Pan[2,3,4]

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

年份：2023

卷号：3

期号：11

起止页码：2964

外文期刊名：JACS AU

收录：WOS:【ESCI(收录号:WOS:001141331300001)】；

基金：We thank Jianan Li and Shengshuo Xu for their generous support. This work was financially supported by grants from the National Key Research and Development Program of China (Nos. 2019YFC1906700, 2019YFC1604602, and 2022YFA1503503), the National Natural Science Foundation of China (Nos. 22222602, 22006039, 21876049, 21972023, 21773032, and 22022301), China Postdoctoral Science Foundation (2019M661412), Strategic Priority Research Program of the Chinese Academy of Sciences (XDA23010400), and the Innovation Program from CECEP China (cecep-zdkj-2021-006).

语种：英文

外文关键词：Nickel peroxide; Structureprediction; Superoxide; Oxygen species; Electrochemistry

摘要：Nickel peroxides are a class of stoichiometric oxidants that can selectively oxidize various organic compounds, but their molecular level structure remained elusive until now. Herein, we utilized structural prediction using the Stochastic Surface Walking method based on a neural network potential energy surface and advanced characterization using the as-synthesized nickel peroxide to unravel its chemical identity as the bridging superoxide containing nickel hydroxide, or nickel superoxyhydroxide. Superoxide incorporation tunes the local chemical environment of nickel and oxygen beyond the conventional Bode plot, offering a 6.4-fold increase in the electrocatalytic activity of urea oxidation. A volcanic dependence of the activity on the oxygen equivalents leads to the proposed active site of the Ni-(OO)-(OH)Ni five-membered ring. This work not only unveils the possible structures of nickel peroxides but also emphasizes the significance of tailoring the oxygen environment for advanced catalysis.