文献类型：期刊文献

英文题名：In Situ Loading of Cu2O Active Sites on Island-like Copper for Efficient Electrochemical Reduction of Nitrate to Ammonia

作者：Wang, Chaochen[1];Ye, Fan[2];Shen, Jianhua[1];Xue, Kan-Hao[2];Zhu, Yihua[1];Li, Chunzhong[1]

机构：[1]East China Univ Sci & Technol, Shanghai Engn Res Ctr Hierarch Nanomat, Sch Mat Sci & Engn, Key Lab Ultrafine Mat,Minist Educ, Shanghai 200237, Peoples R China;[2]Huazhong Univ Sci & Technol, Sch Opt & Elect Informat, Wuhan Natl Lab Optoelect, Wuhan 430074, Peoples R China

年份：2022

卷号：14

期号：5

起止页码：6680

外文期刊名：ACS APPLIED MATERIALS & INTERFACES

收录：;EI(收录号：20220611606309);WOS:【SCI-EXPANDED(收录号:WOS:000768699400034)】；

基金：This work was supported by the National Natural Science Foundation of China (21978087, 22178106, 21776092, 21838003, and 91834301), the Shanghai Scientific and Technological Innovation Project (19JC1410400 and 18JC1410600), the Innovation Program of Shanghai Municipal Education Commission, Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutes of High Learning, and the Fundamental Research Funds for the Central Universities (222201718002).

语种：英文

外文关键词：nitrate electroreduction; island-like copper; in situ electroreduction; in situ Raman

摘要：Electrochemical nitrate reduction reaction (NO3RR) offers a new pathway for low-temperature green ammonia synthesis. It is widely known that copper and its copper oxide catalysts are selective for NO(3)RRs, although the role played by their oxidation state in catalysis is not fully understood. Here, we found that in situ electrochemical reduction modulates the oxidation state of copper facilitating in situ loading of Cu2O active sites on island-like copper, and investigated the effect of cuprous oxide on nitrate reduction. We found that the improvement of ammonia yield (Faraday efficiency: 98.28%, selectivity: 96.6%) was closely related to the generation of Cu2O, which exceeded the performance of the state-of-the-art catalysts available today. The presence of a multilayer structure of the material was demonstrated by X-ray photoelectron spectroscopy combined with ion beam sputtering. Using operando Raman spectroscopy, we monitored the reduction process of the catalyst surface oxide species at the applied potential. Density functional theory (DFT) calculations indicated that the stable presence of Cu(I) effectively promotes the conversion of *HNOH to *HNHOH. We optimized the model building for DFT calculations and established relatively more reliable reaction paths, which provided a strong support for a further understanding of the reaction mechanism of NO3RR.