Photoelectrochemical(PEC)H_(2)O_(2)production through water oxidation reaction(WOR)is a promising strategy,however,designing highly efficient and selective photoanode materials remains challenging due to competitive r...Photoelectrochemical(PEC)H_(2)O_(2)production through water oxidation reaction(WOR)is a promising strategy,however,designing highly efficient and selective photoanode materials remains challenging due to competitive reaction pathways.Here,for highly enhanced PEC H_(2)O_(2)production,we present a conformal amorphous titanyl phosphate(a-TP)overlayer on nanoparticulate TiO_(2)surfaces,achieved via lysozyme-molded in-situ surface reforming.The a-TP overlayer modulates surface adsorption energies for reaction intermediates,favoring WOR for H_(2)O_(2)production over the competing O_(2)evolution reaction.Our density functional theory calculations reveal that a-TP/TiO_(2)exhibits a substantial energy uphill for the O·*formation pathway,which disfavors O_(2)evolution but promotes H_(2)O_(2)production.Additionally,the a-TP overlayer strengthens the built-in electric field,resulting in favorable kinetics.Consequently,a-TP/TiO_(2)exhibits 3.7-fold higher Faraday efficiency(FE)of 63%at 1.76 V vs.reversible hydrogen electrode(RHE)under 1 sun illumination,compared to bare TiO_(2)(17%),representing the highest FE among TiO_(2)-based WOR H_(2)O_(2)production systems.Employing the a-TP overlayer constitutes a promising strategy for controlling reaction pathways and achieving efficient solar-to-chemical energy conversion.展开更多
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government,Ministry of Science and ICT(MSIT)(NRF-2020M3D1A2102837)the Korea Institute of Energy Technology Evaluation and Planning(KETEP)grant funded by the Korea government(MOTIE)(20214000000500,training program of CCUS for the green growth)。
文摘Photoelectrochemical(PEC)H_(2)O_(2)production through water oxidation reaction(WOR)is a promising strategy,however,designing highly efficient and selective photoanode materials remains challenging due to competitive reaction pathways.Here,for highly enhanced PEC H_(2)O_(2)production,we present a conformal amorphous titanyl phosphate(a-TP)overlayer on nanoparticulate TiO_(2)surfaces,achieved via lysozyme-molded in-situ surface reforming.The a-TP overlayer modulates surface adsorption energies for reaction intermediates,favoring WOR for H_(2)O_(2)production over the competing O_(2)evolution reaction.Our density functional theory calculations reveal that a-TP/TiO_(2)exhibits a substantial energy uphill for the O·*formation pathway,which disfavors O_(2)evolution but promotes H_(2)O_(2)production.Additionally,the a-TP overlayer strengthens the built-in electric field,resulting in favorable kinetics.Consequently,a-TP/TiO_(2)exhibits 3.7-fold higher Faraday efficiency(FE)of 63%at 1.76 V vs.reversible hydrogen electrode(RHE)under 1 sun illumination,compared to bare TiO_(2)(17%),representing the highest FE among TiO_(2)-based WOR H_(2)O_(2)production systems.Employing the a-TP overlayer constitutes a promising strategy for controlling reaction pathways and achieving efficient solar-to-chemical energy conversion.
