The slow-proton-fast-electron process severely limits the catalytic efficiency of oxygen evolution reaction.A method is proposed to accelerate proton transfer by building up local electric fields.Modifying acetic,etha...The slow-proton-fast-electron process severely limits the catalytic efficiency of oxygen evolution reaction.A method is proposed to accelerate proton transfer by building up local electric fields.Modifying acetic,ethanedioic and propanetricarboxylic(C_(6)H_(8)O_(6))ligands on BiVO_(4)surface results in a potential difference between BiVO_(4)and ligands that generates a local electric field which serves as a driving force for proton transfer.Among the ligands,carrying the strongest electron-withdrawing ability,the modification of C_(6)H_(8)O_(6) forms the strongest local electric field and leads to the fastest proton transfer and the smallest thermodynamic overpotential.C_(6)H_(8)O_(6)-BiVO_(4)exhibits 3.5 times photocurrent density as high as that of pure BiVO_(4),which is 3.50 mA cm^(-2)at 1.23 VRHE.The onset potential of C_(6)H_(8)O_(6)-BiVO_(4)shifts negatively from 0.70 to 0.38 VRHE.The mechanism for OER transitions from thermodynamically high energy proton-coupled electron transfer to thermodynamically low energy electron transfer as proton transfer is accelerated.展开更多
文摘The slow-proton-fast-electron process severely limits the catalytic efficiency of oxygen evolution reaction.A method is proposed to accelerate proton transfer by building up local electric fields.Modifying acetic,ethanedioic and propanetricarboxylic(C_(6)H_(8)O_(6))ligands on BiVO_(4)surface results in a potential difference between BiVO_(4)and ligands that generates a local electric field which serves as a driving force for proton transfer.Among the ligands,carrying the strongest electron-withdrawing ability,the modification of C_(6)H_(8)O_(6) forms the strongest local electric field and leads to the fastest proton transfer and the smallest thermodynamic overpotential.C_(6)H_(8)O_(6)-BiVO_(4)exhibits 3.5 times photocurrent density as high as that of pure BiVO_(4),which is 3.50 mA cm^(-2)at 1.23 VRHE.The onset potential of C_(6)H_(8)O_(6)-BiVO_(4)shifts negatively from 0.70 to 0.38 VRHE.The mechanism for OER transitions from thermodynamically high energy proton-coupled electron transfer to thermodynamically low energy electron transfer as proton transfer is accelerated.
