The electrochemical reduction of NO_(3)^(−)to NH_(3)represents a promising approach for producing a renewable fuel with high energy density.However,problems such as low activity and/or selectivity in low-concentration...The electrochemical reduction of NO_(3)^(−)to NH_(3)represents a promising approach for producing a renewable fuel with high energy density.However,problems such as low activity and/or selectivity in low-concentration solutions(≤100 ppm NO_(3)^(−)-N)and instability of active sites still require to be overcome.In this work,Cu/ZnO heterostructure composite materials were synthesized for the NO_(3)RR.During the electrocatalysis process,Cu/ZnO undergoes electrochemistry-driven structural reconstruction,generating the CuZn bimetallic alloy phase.In a dilute NO_(3)^(−)-N solution of 100 ppm,the optimal Cu_(75)Zn_(25)catalyst exhibits an FENH_(3)of 94.1%at−0.7 V vs.RHE,and a high NH_(3)yield of 414 mmol h^(−1)g_(cat)^(−1).Density functional theory calculations and a series of characterization studies unveiled that the CuZn alloy phase alters the electronic state surrounding Cu,leading to the regulation of the Cu d-band center and thereby optimizing the adsorption of intermediates.Meanwhile,forming a new alloy phase inhibits the competitive HER as well.This study shows the prospect of the CuZn composite catalyst in sustainable NH_(3)synthesis,which holds a certain guiding significance for the efficient and eco-friendly conversion of effluents in the future.展开更多
基金supported by the National Natural Science Foundation of China(No.22278108 and 22008048)the Natural Science Foundation of Tianjin(22JCYBJC00250 and 23JCQNJC00360)+2 种基金the Natural Science Foundation for Outstanding Youth Scholars of Hebei Province(No.B2024202008)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF2314)the Government Guide the Development of Local Science and Technology Special Funds(246Z4004G).
文摘The electrochemical reduction of NO_(3)^(−)to NH_(3)represents a promising approach for producing a renewable fuel with high energy density.However,problems such as low activity and/or selectivity in low-concentration solutions(≤100 ppm NO_(3)^(−)-N)and instability of active sites still require to be overcome.In this work,Cu/ZnO heterostructure composite materials were synthesized for the NO_(3)RR.During the electrocatalysis process,Cu/ZnO undergoes electrochemistry-driven structural reconstruction,generating the CuZn bimetallic alloy phase.In a dilute NO_(3)^(−)-N solution of 100 ppm,the optimal Cu_(75)Zn_(25)catalyst exhibits an FENH_(3)of 94.1%at−0.7 V vs.RHE,and a high NH_(3)yield of 414 mmol h^(−1)g_(cat)^(−1).Density functional theory calculations and a series of characterization studies unveiled that the CuZn alloy phase alters the electronic state surrounding Cu,leading to the regulation of the Cu d-band center and thereby optimizing the adsorption of intermediates.Meanwhile,forming a new alloy phase inhibits the competitive HER as well.This study shows the prospect of the CuZn composite catalyst in sustainable NH_(3)synthesis,which holds a certain guiding significance for the efficient and eco-friendly conversion of effluents in the future.
