Hematite(α-Fe_(2)O_(3))constitutes one of the most promising photoanode materials for oxygen evolution reaction(OER).Recent research on Fe_(2)O_(3)have found a fast OER rate dependence on surface hole density,suggest...Hematite(α-Fe_(2)O_(3))constitutes one of the most promising photoanode materials for oxygen evolution reaction(OER).Recent research on Fe_(2)O_(3)have found a fast OER rate dependence on surface hole density,suggesting a multisite reaction pathway.However,the effect of heteroatom in Fe_(2)O_(3)on the multisite mechanism is still poorly understood.Herein we synthesized Fe_(2)O_(3)on Ti substrates(Fe_(2)O_(3)/Ti)to study the oxygen intermediates of OER by light-dark electrochemical scans.We identified the Fe-OH species disappeared and Ti-OH intermediates appeared on Fe_(2)O_(3)/Ti when pH=11‒14,which significantly improved the OER performance of Fe_(2)O_(3)/Ti.Combined with the density functional theory calculations,we propose that Ti atom acts as cocatalyst site and captures proton from neighboring Fe-OH species under highly alkaline condition,thereby promoting the coupling of Fe=O and reducing the energy barrier of the non-electrochemical step.Our work provides a new insight into the role of heteroatom in OER multisite mechanism based on clarifying the reaction intermediates.展开更多
文摘Hematite(α-Fe_(2)O_(3))constitutes one of the most promising photoanode materials for oxygen evolution reaction(OER).Recent research on Fe_(2)O_(3)have found a fast OER rate dependence on surface hole density,suggesting a multisite reaction pathway.However,the effect of heteroatom in Fe_(2)O_(3)on the multisite mechanism is still poorly understood.Herein we synthesized Fe_(2)O_(3)on Ti substrates(Fe_(2)O_(3)/Ti)to study the oxygen intermediates of OER by light-dark electrochemical scans.We identified the Fe-OH species disappeared and Ti-OH intermediates appeared on Fe_(2)O_(3)/Ti when pH=11‒14,which significantly improved the OER performance of Fe_(2)O_(3)/Ti.Combined with the density functional theory calculations,we propose that Ti atom acts as cocatalyst site and captures proton from neighboring Fe-OH species under highly alkaline condition,thereby promoting the coupling of Fe=O and reducing the energy barrier of the non-electrochemical step.Our work provides a new insight into the role of heteroatom in OER multisite mechanism based on clarifying the reaction intermediates.
