摘要
Developing low-cost,efficient,and stable non-precious-metal electrocatalysts with controlled crystal structure,morphology and compositions are highly desirable for hydrogen and oxygen evolution reactions.Herein,a series of phosphorus-doped Fe_(7)S_(8)nanowires integrated within carbon(P-Fe_(7)S_(8)@C)are rationally synthesized via a one-step phosphorization of one-dimensional(1D)Fe-based organicinorganic nanowires.The as-obtained P-Fe_(7)S_(8)@C catalysts with modified electronic configurations present typical porous structure,providing plentiful active sites for rapid reaction kinetics.Density functional calculations demonstrate that the doping Fe_(7)S_(8)with P can effectively enhance the electron density of Fe_(7)S_(8)around the Fermi level and weaken the Fe-H bonding,leading to the decrease of adsorption free energy barrier on active sites.As a result,the optimal catalyst of P-Fe_(7)S_(8)-600@C exhibits a relatively low overpotential of 136 mV for hydrogen evolution reaction(HER)to reach the current density of 10 mA/cm^(2),and a significantly low overpotential of 210 mV for oxygen evolution reaction(OER)at 20 mA/cm^(2)in alkaline media.The work presented here may pave the way to design and synthesis of other prominent Fe-based catalysts for water splitting via electronic regulation.
基金
the National Natural Science Foundation of China(Nos.21601120 and 21805181)
the Science and Technology Commission of Shanghai Municipality(Nos.17ZR1410500 and 19ZR1418100)
the High Performance Computing Center of Shanghai University
Shanghai Engineering Research Center of Intelligent Computing System(No.19DZ2252600)for providing the computing resources and technical support。
