Electrocatalytic C–N coupling shows great potential in direct and sustainable urea synthesis.However,the mechanism of interaction between catalytic sites and intermediate species is currently unclear,and exploring co...Electrocatalytic C–N coupling shows great potential in direct and sustainable urea synthesis.However,the mechanism of interaction between catalytic sites and intermediate species is currently unclear,and exploring corresponding strategies to boost urea synthesis is urgent.Herein,we demonstrated that a multihole structure could preserve the Cu^(+)component of Cu_(2)O spheres under electrochemical reduction conditions.An in situ formed Cu^(0)–Cu^(+)site thermodynamically and kinetically promoted the asymmetric coupling process of^(*)CO and^(*)NO,thereby boosting the urea production.The impressive urea yield rates of 29.2 and 114.0 mmol h^(−1)g^(−1)were realized for electrochemical coupling of CO_(2)with nitrate and nitrite,respectively.The multihole-Cu_(2)O exhibits both superior activity and long-term stability compared to the electrocatalysts with a reconstructed Cu^(0)-dominated surface.This work provides insights into the identification and design of the active site for C–N coupling and urea synthesis.展开更多
基金support from the National Key R&D Program of China(grant no.2020YFA0710000)the National Natural Science Foundation of China(grant nos.22102054,21573066,21902047,21825201,U1932212)the China Postdoctoral Science Foundation(grant nos.BX20200116,2020M682540,2021M702228).
文摘Electrocatalytic C–N coupling shows great potential in direct and sustainable urea synthesis.However,the mechanism of interaction between catalytic sites and intermediate species is currently unclear,and exploring corresponding strategies to boost urea synthesis is urgent.Herein,we demonstrated that a multihole structure could preserve the Cu^(+)component of Cu_(2)O spheres under electrochemical reduction conditions.An in situ formed Cu^(0)–Cu^(+)site thermodynamically and kinetically promoted the asymmetric coupling process of^(*)CO and^(*)NO,thereby boosting the urea production.The impressive urea yield rates of 29.2 and 114.0 mmol h^(−1)g^(−1)were realized for electrochemical coupling of CO_(2)with nitrate and nitrite,respectively.The multihole-Cu_(2)O exhibits both superior activity and long-term stability compared to the electrocatalysts with a reconstructed Cu^(0)-dominated surface.This work provides insights into the identification and design of the active site for C–N coupling and urea synthesis.
