Nowadays catalytic nitrogen reduction reaction(NRR)by electrochemistry has attracted much attention because of its key role in producing the basic chemical product ammonia with low energy consumption.A stable and envi...Nowadays catalytic nitrogen reduction reaction(NRR)by electrochemistry has attracted much attention because of its key role in producing the basic chemical product ammonia with low energy consumption.A stable and environmentally‐friendly single‐or multi‐atom catalyst with good performance in activity and selectivity is highly desired for NRR.From density functional theory calculations,the NRR mechanisms catalyzed by Nb monomer,dimer,trimer and tetramer anchored on graphitic carbon nitride(Nb_(x)@g‐C_(3)N_(4),x=1,2,3,4)have been deeply explored.It has been found that Nb_(3)@g‐C_(3)N_(4) exhibits the best catalytic ability among the four catalysts with the introduction of H+.A more stable intermediate(*NH_(2)+*H)can be found to reduce the huge free energy barrier of forming*NH_(3) from*NH_(2) directly in a multi‐atom system.By analyzing the density of states and projected crystal orbital Hamilton population,a synergistic effect among Nb atoms and the adsorbed H^(+)is responsible for reducing the overpotential of NRR.Furthermore,the competitive hydrogen evolution reaction is suppressed effectively.This work introduces a new insight in the reaction pathway in multi‐atoms for developing high‐efficiency NRR catalysts.展开更多
文摘Nowadays catalytic nitrogen reduction reaction(NRR)by electrochemistry has attracted much attention because of its key role in producing the basic chemical product ammonia with low energy consumption.A stable and environmentally‐friendly single‐or multi‐atom catalyst with good performance in activity and selectivity is highly desired for NRR.From density functional theory calculations,the NRR mechanisms catalyzed by Nb monomer,dimer,trimer and tetramer anchored on graphitic carbon nitride(Nb_(x)@g‐C_(3)N_(4),x=1,2,3,4)have been deeply explored.It has been found that Nb_(3)@g‐C_(3)N_(4) exhibits the best catalytic ability among the four catalysts with the introduction of H+.A more stable intermediate(*NH_(2)+*H)can be found to reduce the huge free energy barrier of forming*NH_(3) from*NH_(2) directly in a multi‐atom system.By analyzing the density of states and projected crystal orbital Hamilton population,a synergistic effect among Nb atoms and the adsorbed H^(+)is responsible for reducing the overpotential of NRR.Furthermore,the competitive hydrogen evolution reaction is suppressed effectively.This work introduces a new insight in the reaction pathway in multi‐atoms for developing high‐efficiency NRR catalysts.
