Developing low-priced,yet effective and robust catalysts for the nitrogen reduction reaction(NRR) is of vital importance for scalable and renewable electrochemical NH3 synthesis.Herein,we provide the first demonstrati...Developing low-priced,yet effective and robust catalysts for the nitrogen reduction reaction(NRR) is of vital importance for scalable and renewable electrochemical NH3 synthesis.Herein,we provide the first demonstration of MoS_3 as an efficient and durable NRR catalyst in neutral media.The prepared amorphous MoS_3 naturally possessed enriched S vacancies and delivered an NH3 yield of 51.7 μg h^(-1) mg^(-1)and a Faradaic efficiency of 12.8% at-0.3 V(RHE) in 0.5 M LiClO_4,considerably exceeding those of MoS_2 and most reported NRR catalysts.Density functional theory calculations unraveled that S vacancies involved in MoS_3 played a crucial role in activating the NRR via a consecutive mechanism with a low energetics barrier and simultaneously suppressing the hydrogen evolution reaction.展开更多
Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is...Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is vital to improve the kinetics of ammonia synthesis and obtain a less energy-intensive process.Herein,carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6) was prepared and applied as an electrocatalyst for high-efficiency NRR.A dramatic faradaic efficiency(FE)of 36.93%and an NH_(3) production rate of 13.1μg h^(-1) mg_(cat)^(-1) were obtained at-0.3 V versus RHE,superior to nearly all Fe-based catalysts.Experiments and DFT calculations revealed that the superior performance was ascribed to the synergistic effect of mixed-valence iron pair,which braked the linear correlations to improve the kinetics of ammonia from collaborative hydrogenation and*NH_(3) separation.This work proves the feasibility of mixedvalence catalysts for nitrogen reduction and thus opening a new avenue towards artificial nitrogenfixation catalysts.展开更多
基金supported by the National Natural Science Foundation of China (51761024)the CAS ‘‘Light of West China” Program+1 种基金‘‘Feitian Scholar” Program of Gansu Provincethe Foundation of A Hundred Youth Talents Training Program of Lanzhou Jiaotong University。
文摘Developing low-priced,yet effective and robust catalysts for the nitrogen reduction reaction(NRR) is of vital importance for scalable and renewable electrochemical NH3 synthesis.Herein,we provide the first demonstration of MoS_3 as an efficient and durable NRR catalyst in neutral media.The prepared amorphous MoS_3 naturally possessed enriched S vacancies and delivered an NH3 yield of 51.7 μg h^(-1) mg^(-1)and a Faradaic efficiency of 12.8% at-0.3 V(RHE) in 0.5 M LiClO_4,considerably exceeding those of MoS_2 and most reported NRR catalysts.Density functional theory calculations unraveled that S vacancies involved in MoS_3 played a crucial role in activating the NRR via a consecutive mechanism with a low energetics barrier and simultaneously suppressing the hydrogen evolution reaction.
基金supported by the National Natural Science Foundation of China(21908120 and 22109078)the Youth Innovation Team Project of Shandong Provincial Education Department(2019KJC023)。
文摘Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is vital to improve the kinetics of ammonia synthesis and obtain a less energy-intensive process.Herein,carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6) was prepared and applied as an electrocatalyst for high-efficiency NRR.A dramatic faradaic efficiency(FE)of 36.93%and an NH_(3) production rate of 13.1μg h^(-1) mg_(cat)^(-1) were obtained at-0.3 V versus RHE,superior to nearly all Fe-based catalysts.Experiments and DFT calculations revealed that the superior performance was ascribed to the synergistic effect of mixed-valence iron pair,which braked the linear correlations to improve the kinetics of ammonia from collaborative hydrogenation and*NH_(3) separation.This work proves the feasibility of mixedvalence catalysts for nitrogen reduction and thus opening a new avenue towards artificial nitrogenfixation catalysts.
