Catalytic reduction of molecular dinitrogen(N_(2))to ammonia(NH_(3))is one of the most important and challenging industrial reactions.Electrochemical reduction is considered as an energy-saving technology for artifici...Catalytic reduction of molecular dinitrogen(N_(2))to ammonia(NH_(3))is one of the most important and challenging industrial reactions.Electrochemical reduction is considered as an energy-saving technology for artificial ambient nitrogen fixation,which is emerging as an optimal potential sustainable strategy to substitute for the Haber–Bosch process.However,this process demands efficient catalysts for the N_(2)reduction reaction(NRR).Here,by means of first-principles calculations,we systematically explored the potential electrocatalytic performance of single transition metal atoms(Pd,Ag,Rh,Cu,Ti,Mo,Mn,Zn,Fe,Co,Ru,and Pt)embedded in monolayer defective boron phosphide(TMs/BP)monolayer with a phosphorus monovacancy for ambient NH_(3)production.Among them,the Mo/BP exhibits the best catalytic performance for ambient reduction of N_(2)through the typical enzymatic and consecutive reaction pathways with an activation barrier of 0.68 e V,indicating that Mo/BP is an efficient catalyst for N_(2)fixation.We believe that this work could provide a new avenue of ambient NH_(3)synthesis by using the designed single-atom electrocatalysts.展开更多
基金supported by the National Natural Science Foundation of China(51425301,U1601214,51573013,51773092 and 51772147,21475041,21675050,20405142,21305041)Research Foundation of State Key Lab(ZK201805)the Hunan Provincial Innovation Foundation for Postgraduate(Grant No.CX2018B294)
文摘Catalytic reduction of molecular dinitrogen(N_(2))to ammonia(NH_(3))is one of the most important and challenging industrial reactions.Electrochemical reduction is considered as an energy-saving technology for artificial ambient nitrogen fixation,which is emerging as an optimal potential sustainable strategy to substitute for the Haber–Bosch process.However,this process demands efficient catalysts for the N_(2)reduction reaction(NRR).Here,by means of first-principles calculations,we systematically explored the potential electrocatalytic performance of single transition metal atoms(Pd,Ag,Rh,Cu,Ti,Mo,Mn,Zn,Fe,Co,Ru,and Pt)embedded in monolayer defective boron phosphide(TMs/BP)monolayer with a phosphorus monovacancy for ambient NH_(3)production.Among them,the Mo/BP exhibits the best catalytic performance for ambient reduction of N_(2)through the typical enzymatic and consecutive reaction pathways with an activation barrier of 0.68 e V,indicating that Mo/BP is an efficient catalyst for N_(2)fixation.We believe that this work could provide a new avenue of ambient NH_(3)synthesis by using the designed single-atom electrocatalysts.
