文献类型：期刊文献

英文题名：Insights into the activity of nickel boride/nickel heterostructures for efficient methanol electrooxidation

作者：Qi, Yanbin[1,2];Zhang, Yue[3,4];Yang, Li[3,4];Zhao, Yuhan[2];Zhu, Yihua[2];Jiang, Hongliang[1];Li, Chunzhong[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, Key Lab Ultrafine Mat, Minist Educ, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China;[3]Anhui Univ, Inst Phys Sci, Hefei 230601, Peoples R China;[4]Anhui Univ, Inst Informat Technol, Hefei 230601, Peoples R China

年份：2022

卷号：13

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000836839500002)】；

基金：This work was supported by the National Natural Science Foundation of China (21838003, 91834301, 21978278, 21803063 and 21978087), the Shanghai Scientific and Technological Innovation Project (18JC1410500 and 19JC1410400), and the Fundamental Research Funds for the Central Universities (222201718002). The authors thank the Shanghai synchrotron Radiation Facility (14W1, SSRF), the Beijing Synchrotron Radiation Facility (1W1B and soft-X-ray endstation, BSRF), the Hefei Synchrotron Radiation Facility (Photoemission, Magnetic Circular Dichroism and Catalysis/Surface Science Endstations, Endstations at National Synchrotron Radiation Laboratory).

语种：英文

摘要：Understanding the role of active sites in electrooxidation reactions is important yet challenging. Here, the authors use operando spectroscopies to monitor the effect of methanol concentration on Ni3B/Ni heterostructures during formate production. Designing efficient catalysts and understanding the underlying mechanisms for anodic nucleophile electrooxidation are central to the advancement of electrochemically-driven technologies. Here, a heterostructure of nickel boride/nickel catalyst is developed to enable methanol electrooxidation into formate with a Faradaic efficiency of nearly 100%. Operando electrochemical impedance spectroscopy and in situ Raman spectroscopy are applied to understand the influence of methanol concentration in the methanol oxidation reaction. High concentrations of methanol inhibit the phase transition of the electrocatalyst to high-valent electro-oxidation products, and electrophilic oxygen species (O* or OH*) formed on the electrocatalyst are considered to be the catalytically active species. Additional mechanistic investigation with density functional theory calculations reveals that the potential-determining step, the formation of *CH2O, occurs most favorably on the nickel boride/nickel heterostructure rather than on nickel boride and nickel. These results are highly instructive for the study of other nucleophile-based approaches to electrooxidation reactions and organic electrosynthesis.