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 ch...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.展开更多
基金financially supported by the National Natural Science Foundation of China(NSFC)(22179056,22172018)the Liaoning Revitalization Talents Program(XLYC2002097,1807210)+2 种基金the Key Projects of Liaoning Provincial Education Department(JYTZD2023001)the Fundamental Research Funds for the Central Universities(DUT23LAB611)Yingkou Talents Program。
文摘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.
