The oxygen evolution reaction(OER)has become the barrier of the development and application of next-generation sustainable energy systems due to its extremely sluggish reaction kinetics.One of the fundamental challeng...The oxygen evolution reaction(OER)has become the barrier of the development and application of next-generation sustainable energy systems due to its extremely sluggish reaction kinetics.One of the fundamental challenges is to develop cost-effective and high-efficiency electrocatalysts.Elucidating the dynamic structure evolution of catalysts at electrode-electrolyte interfaces during the reaction is of vital importance for understanding how to activate and sustain electrocatalytic performance.To this end,in situ techniques are invaluable for identifying the active centers together with monitoring the key intermediates under operating conditions.In this review,the latest advances on several cutting-edge in situ methods for characterizing the structure evolution process of OER electrocatalysts are comprehensively summarized.Significantly,a brief overview of active motifs and robust structures during electrocatalysis is provided using multiple in situ correlative techniques,which will contribute to establishing the essential structure-performance relationships and updating the understanding of electrocatalytic mechanisms at unprecedented atomic-scale levels under realistic working conditions.Finally,key challenges and perspectives in this emerging field are highlighted for promoting the design of promising electrocatalysts towards efficient oxygen-associated electrocatalysis and electrosynthesis.展开更多
Heteroatom occupancy plays a key role in the precise modulation of specific material regions by introducing foreign elements into the main material matrix,yet it urgently requires further understanding from a spatial ...Heteroatom occupancy plays a key role in the precise modulation of specific material regions by introducing foreign elements into the main material matrix,yet it urgently requires further understanding from a spatial perspective.Herein,we propose a“satellite atom-spinel crystal”concept by synthesizing model catalysts with Fe atoms strategically positioned at two different spatial positions of spinel Co_(3)O_(4)(satellite-Fe at Co_(3)O_(4)(Fe_((Sat))-Co_(3)O_(4))and Fe-doped Co_(3)O_(4)(Co_(3)Fe(In)O_(4))),through which a new catalytic phenomenon is found.Multidimensional in situ spectroscopies revealed that Fe_((Sat))-Co_(3)O_(4) overcomes the crystal field potential energy(FeSat–O>FeSat–O–CoOh)and exhibits 1%(Fe atom)lower impedance than that of Co_(3)Fe(In)O_(4) due to the resistance-free electron delocalization layer formed in Fe_((Sat))-Co_(3)O_(4),which results in tens of times increase of the turnover frequency and mass activity and then a great reduction in the overpotential by 120 mV when used to catalyze the electrochemical oxygen evolution reaction compared to that of Co_(3)Fe(In)O_(4).Density functional theory calculations further dynamically reveal the mechanisms governing electron itinerancy modulation.This study not only provides valuable insights into the impact of heteroatomic spatial positioning on material properties but also significantly expands our understanding of atomic manipulation.展开更多
基金supported by the National Natural Science Foundation of China(W2412038 and 22241202)the Start-up Fund for the Youth Innovation Talent Project(KY2060000248)+2 种基金the International Partnership Program of Chinese Academy of Sciences(123GJHZ2024102FN)the Natural Science Foundation of Anhui Province(2508085QA016)the China Postdoctoral Science Foundation(GZC20241632 and 2025T180253)。
文摘The oxygen evolution reaction(OER)has become the barrier of the development and application of next-generation sustainable energy systems due to its extremely sluggish reaction kinetics.One of the fundamental challenges is to develop cost-effective and high-efficiency electrocatalysts.Elucidating the dynamic structure evolution of catalysts at electrode-electrolyte interfaces during the reaction is of vital importance for understanding how to activate and sustain electrocatalytic performance.To this end,in situ techniques are invaluable for identifying the active centers together with monitoring the key intermediates under operating conditions.In this review,the latest advances on several cutting-edge in situ methods for characterizing the structure evolution process of OER electrocatalysts are comprehensively summarized.Significantly,a brief overview of active motifs and robust structures during electrocatalysis is provided using multiple in situ correlative techniques,which will contribute to establishing the essential structure-performance relationships and updating the understanding of electrocatalytic mechanisms at unprecedented atomic-scale levels under realistic working conditions.Finally,key challenges and perspectives in this emerging field are highlighted for promoting the design of promising electrocatalysts towards efficient oxygen-associated electrocatalysis and electrosynthesis.
基金supported by the National Natural Science Foundation of China(12405368,12135012)the Natural Science Foundation of Anhui Province(2408085QA016)the Scholarship from the China Scholarship Council(CSC)(202306340088)。
文摘Heteroatom occupancy plays a key role in the precise modulation of specific material regions by introducing foreign elements into the main material matrix,yet it urgently requires further understanding from a spatial perspective.Herein,we propose a“satellite atom-spinel crystal”concept by synthesizing model catalysts with Fe atoms strategically positioned at two different spatial positions of spinel Co_(3)O_(4)(satellite-Fe at Co_(3)O_(4)(Fe_((Sat))-Co_(3)O_(4))and Fe-doped Co_(3)O_(4)(Co_(3)Fe(In)O_(4))),through which a new catalytic phenomenon is found.Multidimensional in situ spectroscopies revealed that Fe_((Sat))-Co_(3)O_(4) overcomes the crystal field potential energy(FeSat–O>FeSat–O–CoOh)and exhibits 1%(Fe atom)lower impedance than that of Co_(3)Fe(In)O_(4) due to the resistance-free electron delocalization layer formed in Fe_((Sat))-Co_(3)O_(4),which results in tens of times increase of the turnover frequency and mass activity and then a great reduction in the overpotential by 120 mV when used to catalyze the electrochemical oxygen evolution reaction compared to that of Co_(3)Fe(In)O_(4).Density functional theory calculations further dynamically reveal the mechanisms governing electron itinerancy modulation.This study not only provides valuable insights into the impact of heteroatomic spatial positioning on material properties but also significantly expands our understanding of atomic manipulation.
