Stabilizing Cu^(+)active sites by small molecule modulation on copper electrocatalyst for boosting semi-hydrogenation of alkynes in water  

作　　者：Ran Li Hui Li Jing Luo Jie Zhou Qi Sui Yujie Gao Hongshuai Zheng Lixin Xia Fei Li Yi Jiang 

机构地区：[1]College of Chemistry,Liaoning University,Shenyang 110036,Liaoning,China [2]YingKou Institute of Technology,Yingkou 115014,Liaoning,China [3]State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,Liaoning,China

出　　处：《Journal of Energy Chemistry》2025年第3期800-807,共8页能源化学(英文版)

基　　金：financially supported by the National Natural Science Foundation of China(NSFC)(22179056,22172018);the Liaoning Revitalization Talents Program(XLYC2002097,1807210);the Key Projects of Liaoning Provincial Education Department(JYTZD2023001);the Fundamental Research Funds for the Central Universities(DUT23LAB611);Yingkou Talents Program。

摘　　要：Selective electrocatalytic semi-hydrogenation(ECSH)of alkynes in water using Cu catalysts is highly relevant for the production of value-added chemicals.However,achieving high olefin selectivity still poses extreme challenges due to the susceptibility of the copper cathode in a reduction environment.Herein,a small molecule modulation electrodeposition strategy is introduced that regulates the structure of Cubased materials through modification with citric acid(CA)ligands,aiming for highly active and selective ECSH.The as-prepared EDCu-CA electrode achieves more than 97%alkyne conversion and 99%olefin selectivity.In-situ Raman and Auger electron spectroscopy(AES)data provide evidence that active Cu^(+)sites can stably exist in the EDCu-CA during the catalytic process.Density functional theory(DFT)calculations indicate that the modulation by CA contributes to maintaining Cu in a positive valence state,and Cu^(+)can inhibit the over-hydrogenation of olefins.Moreover,by utilizing a large-area electrode for longterm electrolysis,g-level conversion and a 92%separation yield of olefin can be achieved,demonstrating a viable application prospect.This study offers a promising route for designing Cu-based catalysts for the highly selective electrocata lytic conversion of organic substrates to value-added chemicals in water.

关 键 词：Electrocatalysis Cu catalysts Alkyne semi-hydrogenation Citric acid modulation Stabilizing Cu+ 

分 类 号：O643.36[理学—物理化学]