Urea synthesis through the simultaneous electrocatalytic reduction of N_(2)and CO_(2)molecules under ambient conditions holds great promises as a sustainable alternative to its industrial production,in which the devel...Urea synthesis through the simultaneous electrocatalytic reduction of N_(2)and CO_(2)molecules under ambient conditions holds great promises as a sustainable alternative to its industrial production,in which the development of stable,highly efficient,and highly selective catalysts to boost the chemisorption,activation,and coupling of inert N_(2)and CO_(2)molecules remains rather challenging.Herein,by means of density functional theory computations,we proposed a new class of two-dimensional nanomaterials,namely,transition-metal phosphide monolayers(TM_(2)P,TM=Ti,Fe,Zr,Mo,and W),as the potential electrocatalysts for urea production.Our results showed that these TM_(2)P materials exhibit outstanding stability and excellent metallic properties.Interestingly,the Mo_(2)P monolayer was screened out as the best catalyst for urea synthesis due to its small kinetic energy barrier(0.35 eV)for C-N coupling,low limiting potential(-0.39 V),and significant suppressing effects on the competing side reactions.The outstanding catalytic activity of the Mo_(2)P monolayer can be ascribed to its optimal adsorption strength with the key^(*)NCON species due to its moderate positive charges on the Mo active sites.Our findings not only propose a novel catalyst with high-efficiency and high-selectivity for urea production but also further widen the potential applications of metal phosphides in electrocatalysis.展开更多
基金financially supported in China by Natural Science Funds for Distinguished Young Scholars of Heilongjiang Province(No.JC2018004)Natural Science Foundation of Heilongjiang Province of China(No.TD2020B001)in the USA by NSF-CREST Center for Innovation,Research,and Education in Environmental Nanotechnology(CIRE2N)(No.HRD-1736093)
文摘Urea synthesis through the simultaneous electrocatalytic reduction of N_(2)and CO_(2)molecules under ambient conditions holds great promises as a sustainable alternative to its industrial production,in which the development of stable,highly efficient,and highly selective catalysts to boost the chemisorption,activation,and coupling of inert N_(2)and CO_(2)molecules remains rather challenging.Herein,by means of density functional theory computations,we proposed a new class of two-dimensional nanomaterials,namely,transition-metal phosphide monolayers(TM_(2)P,TM=Ti,Fe,Zr,Mo,and W),as the potential electrocatalysts for urea production.Our results showed that these TM_(2)P materials exhibit outstanding stability and excellent metallic properties.Interestingly,the Mo_(2)P monolayer was screened out as the best catalyst for urea synthesis due to its small kinetic energy barrier(0.35 eV)for C-N coupling,low limiting potential(-0.39 V),and significant suppressing effects on the competing side reactions.The outstanding catalytic activity of the Mo_(2)P monolayer can be ascribed to its optimal adsorption strength with the key^(*)NCON species due to its moderate positive charges on the Mo active sites.Our findings not only propose a novel catalyst with high-efficiency and high-selectivity for urea production but also further widen the potential applications of metal phosphides in electrocatalysis.
