Balancing electron transfer and intermediate adsorption ability of bifunctional catalysts via tailoring electronic structures is crucial for green hydrogen production,while it still remains challenging due to lacking ...Balancing electron transfer and intermediate adsorption ability of bifunctional catalysts via tailoring electronic structures is crucial for green hydrogen production,while it still remains challenging due to lacking efficient strategies.Herein,one efficient and universal strategy is developed to greatly regulate electronic structures of the metallic Ni-Fe-P catalysts via in-situ introducing the rare earth(RE)atoms(Ni-Fe-RE-P,RE=La,Ce,Pr,and Nd).Accordingly,the as-prepared optimal Ni-Fe-Ce-P/CC self-supported bifunctional electrodes exhibited superior electrocatalytic activity and excellent stability with the low overpotentials of 247 and 331 mV at 100 mA cm^(-2) for HER and OER,respectively.In the assembled electrolyzer,the Ni-Fe-Ce-P/CC as bifunctional electrodes displayed low operation potential of 1.49 V to achieve a current density of 10 mA cm^(-2),and the catalytic performance can be maintained for 100 h.Experimental results combined with density functional theory(DFT)calculation reveal that Ce doping leads to electron decentralization and crystal structure distortion,which can tailor the band structures and d-band center of Ni-Fe-P,further increasing conductivity and optimizing intermediate adsorption energy.Our work not only proposes a valuable strategy to regulate the electron transfer and intermediate adsorption of electrocatalysts via RE atoms doping,but also provides a deep under-standing of regulation mechanism of metallic electrocatalysts for enhanced water splitting.展开更多
Stabilizing the highly active RuO_(2) electrocatalyst for the oxygen evolution reaction(OER)is critical for the application of proton exchange membrane water electrolysis,but this remains challenging due to the inevit...Stabilizing the highly active RuO_(2) electrocatalyst for the oxygen evolution reaction(OER)is critical for the application of proton exchange membrane water electrolysis,but this remains challenging due to the inevitable over-oxidation of Ru in harsh oxidative environments.Herein,we describe constructing Ru-O-La asymmetric configurations into RuO_(2) via a facile sol-gel method to tailor electron redistribution and thereby eliminate the over-oxidation of Ru centers.Specifically,the as-prepared optimal La_(0.1)Ru_(0.9)O_(2) shows a low overpotential of 188 mV at 10 mA cm^(-2),a high mass activity of 251 A gRu^(-1) at 1.6 V vs.reversible hydrogen electrode(RHE),and a long-lasting durability of 63 h,far superior to the 8 h achieved by standard RuO_(2).Experiments and density functional theory calculations jointly reveal that the Ru-O-La asymmetric configuration could trigger electron redistribution in RuO_(2).More importantly,electron transfer from La to Ru via the Ru-O-La configuration could lead to increased electron density around Ru,thus preventing the over-oxidation of Ru.In addition,electron redistribution tunes the Ru 4d band center’s energy level,which optimizes the adsorption and desorption of oxygen intermediates.This work offers an effective strategy for regulating electronic structure to synergistically boost the activity and stability of RuO_(2)-based acidic OER electrocatalysts.展开更多
基金support from the National Key Technology R&D Program of China(2021YFB3500801,2022YFC3901503,2022YFB3504302)the Natural Science Foundation and Overseas Talent Projects of Jiangxi Province(20232BAB214025,20232BCJ25044).
文摘Balancing electron transfer and intermediate adsorption ability of bifunctional catalysts via tailoring electronic structures is crucial for green hydrogen production,while it still remains challenging due to lacking efficient strategies.Herein,one efficient and universal strategy is developed to greatly regulate electronic structures of the metallic Ni-Fe-P catalysts via in-situ introducing the rare earth(RE)atoms(Ni-Fe-RE-P,RE=La,Ce,Pr,and Nd).Accordingly,the as-prepared optimal Ni-Fe-Ce-P/CC self-supported bifunctional electrodes exhibited superior electrocatalytic activity and excellent stability with the low overpotentials of 247 and 331 mV at 100 mA cm^(-2) for HER and OER,respectively.In the assembled electrolyzer,the Ni-Fe-Ce-P/CC as bifunctional electrodes displayed low operation potential of 1.49 V to achieve a current density of 10 mA cm^(-2),and the catalytic performance can be maintained for 100 h.Experimental results combined with density functional theory(DFT)calculation reveal that Ce doping leads to electron decentralization and crystal structure distortion,which can tailor the band structures and d-band center of Ni-Fe-P,further increasing conductivity and optimizing intermediate adsorption energy.Our work not only proposes a valuable strategy to regulate the electron transfer and intermediate adsorption of electrocatalysts via RE atoms doping,but also provides a deep under-standing of regulation mechanism of metallic electrocatalysts for enhanced water splitting.
基金support from the National Key Technology R&D Program of China(2022YFB3504302,2022YFC3-901503)Natural Science Foundation and Overseas Talent Projects of Jiangxi Province(20232BAB214025,20232BCJ25044)Self-deployed Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(E355F003).
文摘Stabilizing the highly active RuO_(2) electrocatalyst for the oxygen evolution reaction(OER)is critical for the application of proton exchange membrane water electrolysis,but this remains challenging due to the inevitable over-oxidation of Ru in harsh oxidative environments.Herein,we describe constructing Ru-O-La asymmetric configurations into RuO_(2) via a facile sol-gel method to tailor electron redistribution and thereby eliminate the over-oxidation of Ru centers.Specifically,the as-prepared optimal La_(0.1)Ru_(0.9)O_(2) shows a low overpotential of 188 mV at 10 mA cm^(-2),a high mass activity of 251 A gRu^(-1) at 1.6 V vs.reversible hydrogen electrode(RHE),and a long-lasting durability of 63 h,far superior to the 8 h achieved by standard RuO_(2).Experiments and density functional theory calculations jointly reveal that the Ru-O-La asymmetric configuration could trigger electron redistribution in RuO_(2).More importantly,electron transfer from La to Ru via the Ru-O-La configuration could lead to increased electron density around Ru,thus preventing the over-oxidation of Ru.In addition,electron redistribution tunes the Ru 4d band center’s energy level,which optimizes the adsorption and desorption of oxygen intermediates.This work offers an effective strategy for regulating electronic structure to synergistically boost the activity and stability of RuO_(2)-based acidic OER electrocatalysts.
