Conventional electrocatalytic urea synthesis via CO_(2)+N_(2) or CO_(2)+NO_(3)^(-)coelectrolysis generally suffers from poor reactants coactivation,low C-N coupling efficiency,and serious competing reactions.To overco...Conventional electrocatalytic urea synthesis via CO_(2)+N_(2) or CO_(2)+NO_(3)^(-)coelectrolysis generally suffers from poor reactants coactivation,low C-N coupling efficiency,and serious competing reactions.To overcome these limitations,we implement HCOOH+NO_(3)^(-)coelectrolysis to urea using a Fe-Pd dual-atom catalyst(Fe_(1)Pd_(1)-DAC).Operando spectroscopic measurements and theoretical computations collectively reveal that Pd_(1) selectively dehydrogenates HCOOH to^(*)COOH,while Fe_(1) selectively activates NO_(3)^(-)to^(*)NH_(2).Specifically,the spatial proximity and electrophilic-nucleophilic synergy of^(*)COOH and^(*)NH_(2) enable the high C-N coupling efficiency and well-suppressed competing reactions.Consequently,Fe_(1)Pd_(1)-DAC assembled in a flow cell delivers the unprecedented urea yield rate up to 448.1 mmol h^(-1) g^(-1) and Faradaic efficiency of 78.3%at an industrial-level current density of-215 mA cm^(-2),far outperforming those obtained from CO_(2)+N_(2) or CO_(2)+NO_(3) coelectrolysis.Further techno-economic analysis demonstrates Fe_(1)Pd_(1)-DAC as a promising catalyst for economically feasible urea production via HCOOH+NO_(3)^(-)coelectrolysis.展开更多
基金supported by the National Natural Science Foundation of China(52561042)the Industrial Support Plan Project of Gansu Provincial Education Department(2024CYZC-22)。
文摘Conventional electrocatalytic urea synthesis via CO_(2)+N_(2) or CO_(2)+NO_(3)^(-)coelectrolysis generally suffers from poor reactants coactivation,low C-N coupling efficiency,and serious competing reactions.To overcome these limitations,we implement HCOOH+NO_(3)^(-)coelectrolysis to urea using a Fe-Pd dual-atom catalyst(Fe_(1)Pd_(1)-DAC).Operando spectroscopic measurements and theoretical computations collectively reveal that Pd_(1) selectively dehydrogenates HCOOH to^(*)COOH,while Fe_(1) selectively activates NO_(3)^(-)to^(*)NH_(2).Specifically,the spatial proximity and electrophilic-nucleophilic synergy of^(*)COOH and^(*)NH_(2) enable the high C-N coupling efficiency and well-suppressed competing reactions.Consequently,Fe_(1)Pd_(1)-DAC assembled in a flow cell delivers the unprecedented urea yield rate up to 448.1 mmol h^(-1) g^(-1) and Faradaic efficiency of 78.3%at an industrial-level current density of-215 mA cm^(-2),far outperforming those obtained from CO_(2)+N_(2) or CO_(2)+NO_(3) coelectrolysis.Further techno-economic analysis demonstrates Fe_(1)Pd_(1)-DAC as a promising catalyst for economically feasible urea production via HCOOH+NO_(3)^(-)coelectrolysis.
