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
Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-...Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.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.
基金supported by the National Natural Science Foundation of China(21403070 and 21373088)Innovation Program of Shanghai Municipal Education Commission(13zz038)+2 种基金Key Project of the Shanghai Committee of Science and Technology(12JC1403600)National Key Technology R&D Program(2012BAE05B02)Shanghai Leading Academic Discipline Project(B409)~~
文摘Small-crystal TS-1 was synthesized via a seed-induced approach using ammonia as the alkali source and tetrapropylammonium bromide as an auxiliary structure-directing agent. The TS-1 samples were characterized using X-ray diffraction, N2 adsorption-desorption, Fourier-transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, and ultraviolet-visible spectroscopy. The use of the colloidal seed reduced the crystal size, and an appropriate amount of silicalite-1 seed assisted Ti incorporation into the TS-1 framework. This method reduces the cost of TS- 1 synthesis because a significantly smaller amount of tetrapropylammonium hydroxide is used. The catalytic performance of the synthesized small-crystal TS-1 samples in cyclohexanone ammoximation was better than that of bulk TS-1 as a result of improved diffusion and a larger number of active tetrahedral Ti centers.
