Nickel(Ni)is a promising catalyst for electrochemical urea oxidation reactions.However,its strong chemisorption of CO_(2) and the tendency for uncontrollable structural reconstruction during catalysis have limited the...Nickel(Ni)is a promising catalyst for electrochemical urea oxidation reactions.However,its strong chemisorption of CO_(2) and the tendency for uncontrollable structural reconstruction during catalysis have limited the exploration of Ni-based catalysts in electrocatalytic urea synthesis.Herein,we propose a comodification strategy for Ni-mSiO_(x) using polydopamine(PDA)and polyethyleneimine(PEI)to enable efficient electrocatalytic co-reduction of nitrate and CO_(2) for urea synthesis.The incorporation of stable Ni-O-Si active sites effectively balanced competing reaction pathways,while dual polymer modification optimized the surface electronic structure,promoted the formation of pyrrolic/pyridinic nitrogen species(ProN/PN,86.7%),and accelerated C-N coupling kinetics.The resulting PDA/PEI-Ni-mSiO_(x) catalyst achieved a urea production rate of 2513μg·h^(−1) ·mg_(cay)^(−1) ,a Faradaic efficiency of 28.6%,and a urea selectivity of 54.2%.Notably,the catalyst retained over 90%of its activity after 39 h of continuous operation,with no observable structural degradation following repeated cycling.This work presents a robust strategy for the rational design of high-performance,durable Ni-based catalysts for urea electrosynthesis and provides mechanistic insights into the structure-activity relationships at polymer-metal oxide interfaces.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21872034,22021001,and 92472203)the Natural Science Foundation of Fujian Province(Nos.2025J01363,2024J01807,and 2025J01973)+1 种基金the Natural Science Foundation of Zhangzhou City(No.ZZ2024J16)the Eagle Project of Fujian Province.
文摘Nickel(Ni)is a promising catalyst for electrochemical urea oxidation reactions.However,its strong chemisorption of CO_(2) and the tendency for uncontrollable structural reconstruction during catalysis have limited the exploration of Ni-based catalysts in electrocatalytic urea synthesis.Herein,we propose a comodification strategy for Ni-mSiO_(x) using polydopamine(PDA)and polyethyleneimine(PEI)to enable efficient electrocatalytic co-reduction of nitrate and CO_(2) for urea synthesis.The incorporation of stable Ni-O-Si active sites effectively balanced competing reaction pathways,while dual polymer modification optimized the surface electronic structure,promoted the formation of pyrrolic/pyridinic nitrogen species(ProN/PN,86.7%),and accelerated C-N coupling kinetics.The resulting PDA/PEI-Ni-mSiO_(x) catalyst achieved a urea production rate of 2513μg·h^(−1) ·mg_(cay)^(−1) ,a Faradaic efficiency of 28.6%,and a urea selectivity of 54.2%.Notably,the catalyst retained over 90%of its activity after 39 h of continuous operation,with no observable structural degradation following repeated cycling.This work presents a robust strategy for the rational design of high-performance,durable Ni-based catalysts for urea electrosynthesis and provides mechanistic insights into the structure-activity relationships at polymer-metal oxide interfaces.
