A conformal titanyl phosphate amorphous overlayer for enhancing photoelectrochemical hydrogen peroxide production  

作　　者：Jaekyum Kim Young Eun Kim Minyeong Je Won Tae Hong Chang-Lyoul Lee Tae-Hoon Kim Sung Min Cho Chang Hyuck Choi Heechae Choi Woo-Seok Choe Jung Kyu Kim 

机构地区：[1]School of Chemical Engineering,Sungkyunkwan University(SKKU),Suwon 16419,Republic of Korea [2]SKKU Advanced Institute of Nano Technology(SAINT),Sungkyunkwan University(SKKU),Suwon 16419,Republic of Korea [3]Theoretical Materials&Chemistry Group,Institute of Inorganic Chemistry,University of Cologne,Greinstr.6,50939,Cologne,Germany [4]Advanced Photonics Research Institute(APRI),Gwangju Institute of Science and Technology(GIST),Gwangju 61005,Republic of Korea [5]Department of Materials Science and Engineering,Chonnam National University,Gwangju 61186,Republic of Korea [6]Department of Chemistry,Pohang University of Science and Technology(POSTECH),Pohang 37673,Republic of Korea [7]Institute for Convergence Research and Education in Advanced Technology(I-CREATE),Yonsei University,Seoul 03722,Republic of Korea [8]Department of Chemistry,Xi’an Jiaotong-Liverpool University,Suzhou 215123,Jiangsu,China

出　　处：《Journal of Energy Chemistry》2023年第11期399-408,I0009,共11页能源化学（英文版）

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)。

摘　　要：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.

关 键 词：Solar H_(2)O_(2) production In-situ surface reforming Titanyl phosphate Amorphous overlayer Reaction pathway control 

分 类 号：TQ123.6[化学工程—无机化工]