Constructing electrocatalytic overall reaction technology to couple the electrosynthesis of adipic acid with energy-saving hydrogen production is of significant for sustainable energy systems.However,the development o...Constructing electrocatalytic overall reaction technology to couple the electrosynthesis of adipic acid with energy-saving hydrogen production is of significant for sustainable energy systems.However,the development of highly-active bifunctional electrocatalysts remains a challenge.Herein,3D hierarchical nickel-copper alloying arrays with dendritic morphology are manufactured by a simple electrodeposition process,standing for the excellent bifunctional electrocatalyst towards the co-production of adipic acid and H_(2)from cyclohexanone and water.The membrane-free flow electrolyzer of Cu_(0.81)Ni_(0.19)/NF shows the superior electrooxidation performance of ketone-alcohol(KA)oil with high faradaic efficiencies of over 90%for adipic acid and H_(2),robust stability over 200 h as well as a high yield of 0.6 mmol h^(-1) for adipic acid at 100 mA cm^(-2).In-situ spectroscopy indicates the Cu_(0.81)Ni_(0.19)alloy contributes to forming more active NiOOH species to involve in the conversion of cyclohexanone to adipic acid,while the proposed reaction pathway undergoes the 2-hydroxycyclohexanone and 2,7-oxepanedione intermediates.Moreover,the theoretical calculations confirm that the optimal electronic interaction,boosted reaction kinetics as well as improved adsorption free energy of reaction intermediates,synergistically endows Cu_(0.81)Ni_(0.19)alloy with superior bifunctional performance.展开更多
基金financially supported by the National Natural Science Foundation of China(22205205,22472151)the Zhejiang Provincial Natural Science Foundation of China(LQ22B030008)the Science Foundation of Zhejiang Sci-Tech University(ZSTU)under Grant No.21062337-Y.
文摘Constructing electrocatalytic overall reaction technology to couple the electrosynthesis of adipic acid with energy-saving hydrogen production is of significant for sustainable energy systems.However,the development of highly-active bifunctional electrocatalysts remains a challenge.Herein,3D hierarchical nickel-copper alloying arrays with dendritic morphology are manufactured by a simple electrodeposition process,standing for the excellent bifunctional electrocatalyst towards the co-production of adipic acid and H_(2)from cyclohexanone and water.The membrane-free flow electrolyzer of Cu_(0.81)Ni_(0.19)/NF shows the superior electrooxidation performance of ketone-alcohol(KA)oil with high faradaic efficiencies of over 90%for adipic acid and H_(2),robust stability over 200 h as well as a high yield of 0.6 mmol h^(-1) for adipic acid at 100 mA cm^(-2).In-situ spectroscopy indicates the Cu_(0.81)Ni_(0.19)alloy contributes to forming more active NiOOH species to involve in the conversion of cyclohexanone to adipic acid,while the proposed reaction pathway undergoes the 2-hydroxycyclohexanone and 2,7-oxepanedione intermediates.Moreover,the theoretical calculations confirm that the optimal electronic interaction,boosted reaction kinetics as well as improved adsorption free energy of reaction intermediates,synergistically endows Cu_(0.81)Ni_(0.19)alloy with superior bifunctional performance.
