Optimized Electronic Modification of S-Doped CuO Induced by Oxidative Reconstruction for Coupling Glycerol Electrooxidation with Hydrogen Evolution

作     者：Ruo‑Yao Fan Xue‑Jun Zhai Wei‑Zhen Qiao Yu‑Sheng Zhang Ning Yu Na Xu Qian‑Xi Lv Yong‑Ming Chai Bin Dong Ruo-Yao Fan;Xue-Jun Zhai;Wei-Zhen Qiao;Yu-Sheng Zhang;Ning Yu;Na Xu;Qian-Xi Lv;Yong-Ming Chai;Bin Dong

作者机构：China State Key Laboratory of Heavy Oil ProcessingCollege of Chemistry and Chemical EngineeringChina University of Petroleum(East China)Qingdao 266580People’s Republic of China 

出 版 物：《Nano-Micro Letters》 (纳微快报（英文版）)

年 卷 期：2023年第15卷第10期

页      面：622-637页

核心收录：

学科分类：081702[工学-化学工艺] 081705[工学-工业催化] 0817[工学-化学工程与技术] 0806[工学-冶金工程] 08[工学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 0703[理学-化学] 

基　　金：financially supported by National Natural Science Foundation of China (52174283 and 52274308) 

主　　题：Glycerol oxidation reaction(GOR) Hydrogen evolution reaction(HER) CuO Oxidative reconstruction Electronic modification 

摘      要：Glycerol(electrochemical) oxidation reaction(GOR) producing organic small molecule acid and coupling with hydrogen evolution reaction is a critical aspect of ensuring balanced glycerol capacity and promoting hydrogen generation on a large scale. However, the development of highly efficient and selective non-noble metal-based GOR electrocatalysts is still a key problem. Here, an S-doped CuO nanorod array catalyst(S-CuO/CF) constructed by sulfur leaching and oxidative remodeling is used to drive GOR at low potentials: It requires potentials of only 1.23 and 1.33 V versus RHE to provide currents of 100 and 500 mA cm^(-2), respectively. Moreover, it shows satisfactory comprehensive performance(at 100 mA cm^(-2), V_(cell) = 1.37 V) when assembled as the anode in asymmetric coupled electrolytic cell. Furthermore, we propose a detailed cycle reaction pathway(in alkaline environment) of S-doped CuO surface promoting GOR to produce formic acid and glycolic acid. Among them, the C–C bond breaking and lattice oxygen deintercalation steps frequently involved in the reaction pathway are the key factors to determine the catalytic performance and product selectivity. This research provides valuable guidance for the development of transition metal-based electrocatalysts for GOR and valuable insights into the glycerol oxidation cycle reaction pathway.