Photoelectrochemical nitrate reduction reaction(PEC-NIRR)is a promising technology of nitrogen fixation,which has the advantages of mild conditions and small carbon footprint.However,due to the low selectivity and com...Photoelectrochemical nitrate reduction reaction(PEC-NIRR)is a promising technology of nitrogen fixation,which has the advantages of mild conditions and small carbon footprint.However,due to the low selectivity and competitive hydrogen evolution reaction(HER),PEC-NIRR still faces a critical challenge to achieve the efficient production of NH_(3).For the first time,in this study,Ce-doped p-BiVO_(4) was fabricated and applied to PEC-NIRR.Ce^(3+)mainly replaced the Bi^(3+)sites in the p-BiVO_(4) matrix,and the reversible redox ability of Ce effectively promoted internal carrier migration and surface catalytic kinetics.Without the externally applied potentials(0 V vs.RHE),1.5%Ce-BiVO_(4) showed desirable activity,and the NH_(3) yield of 1.5%Ce-BiVO_(4) reached 31.54μg h^(-1) cm^(-2),which is 3.9 times that of p-BiVO_(4).The selectivity of NH3(relative to NO_(2)-)was enhanced to 24.5 times,compared with that of pristine p-BiVO_(4).In addition,1H nuclear magnetic resonance(1H NMR)spectroscopy verified that the source of N was entirely NO3-.Therefore,this work identifies the critical role of Ce sites for tailoring the nature of p-BiVO_(4) for efficient PEC-NIRR.展开更多
基金the National Natural Science Foundation of China(22075112)Jiangsu Province and Education Ministry Co-sponsored Synergistic Innovation Center of Modern Agricultural Equipment(XTCX2027).
文摘Photoelectrochemical nitrate reduction reaction(PEC-NIRR)is a promising technology of nitrogen fixation,which has the advantages of mild conditions and small carbon footprint.However,due to the low selectivity and competitive hydrogen evolution reaction(HER),PEC-NIRR still faces a critical challenge to achieve the efficient production of NH_(3).For the first time,in this study,Ce-doped p-BiVO_(4) was fabricated and applied to PEC-NIRR.Ce^(3+)mainly replaced the Bi^(3+)sites in the p-BiVO_(4) matrix,and the reversible redox ability of Ce effectively promoted internal carrier migration and surface catalytic kinetics.Without the externally applied potentials(0 V vs.RHE),1.5%Ce-BiVO_(4) showed desirable activity,and the NH_(3) yield of 1.5%Ce-BiVO_(4) reached 31.54μg h^(-1) cm^(-2),which is 3.9 times that of p-BiVO_(4).The selectivity of NH3(relative to NO_(2)-)was enhanced to 24.5 times,compared with that of pristine p-BiVO_(4).In addition,1H nuclear magnetic resonance(1H NMR)spectroscopy verified that the source of N was entirely NO3-.Therefore,this work identifies the critical role of Ce sites for tailoring the nature of p-BiVO_(4) for efficient PEC-NIRR.
