文献类型：期刊文献

英文题名：A Cosolvent Electrolyte Boosting Electrochemical Alkynol Semihydrogenation

作者：Zhao, Yuan[1,2];Wang, Jia[3,4];Zha, Xingzhou[1];Sheng, Xuedi[1];Dong, Lei[1];Wu, Xin-Ping[3,4];Liu, Zhen[1];Jiang, Hongliang[1];Li, Chunzhong[1,2,5]

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]East China Univ Sci & Technol, Ctr Computat Chem, Sch Chem & Mol Engn, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[5]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Dept Chem Engn, Shanghai 200240, Peoples R China

年份：2025

卷号：147

期号：2

起止页码：1938

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20250317714982);WOS:【SCI-EXPANDED(收录号:WOS:001388631600001)】；

基金：This work was supported by the National Natural Science Foundation of China (22222804 and U22B20143), the National Key R&D program (2022YFB3808400), the Science and Technology Commission of Shanghai Municipality (22dz1205900), and the Shanghai Municipal Science and Technology Major Project.

语种：英文

外文关键词：Dissociation - Electrocatalysis - Electrocatalysts - Electrolysis - Electrolytes - Electropolymerization - Reaction rates

摘要：Green electricity-driven alkenol electrosynthesis via electrocatalytic alkynol semihydrogenation represents a sustainable route to conventional thermocatalysis. Both the electrocatalyst and electrolyte strongly impact the semihydrogenation performance. Despite significant progress in developing sophisticated electrocatalysts, a well-designed electrolyte in conjunction with industrial catalysts is an attractive strategy to advance the industrialization process of electrocatalytic alkynol semihydrogenation, but remains unexplored. Here, we develop a dimethyl sulfoxide (DMSO)-H2O cosolvent electrolyte for electrocatalytic alkynol semihydrogenation. At an alkynol conversion of about 100%, the DMSO-H2O electrolyte compared to the DMSO-free counterpart enables the alkenol selectivity on Cu catalysts to be promoted from 60-70% to over 90% at all measured current densities; meanwhile, the reaction rate is slightly decreased due to the inhibited water dissociation. Mechanistic studies reveal that the strong hydrogen-bond interactions between DMSO and H2O suppress the dissociation of interfacial H2O, leading to a decreased H* coverage at the electrode surface. The decreased H* coverage hinders the overhydrogenation of alkynols and favors the production of alkenols. Remarkably, the DMSO-induced enhancement of alkenol selectivity is applicable to a set of commercial catalysts and to the semihydrogenation of various alkynols. Eventually, a scaled-up 3 x 100 cm2 electrolyzer stack is established to achieve an alkynol conversion of similar to 96% and an alkenol selectivity of similar to 95% in the cosolvent electrolyte. This work not only presents an electrolyte strategy for boosting alkenol electrosynthesis, but also highlights the possibility of sustainable alkenol electro-production.