Surface modification of ZnIn_(2)S_(4)layers to realize energy-transfer-mediated photocatalysis  

作　　者：Xianshun Sun Xiao Luo Sen Jin Xiaodong Zhang Hui Wang Wei Shao Xiaojun Wu Yi Xie 

机构地区：[1]Hefei National Laboratory for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei 230026,China [2]Institute of Energy,Hefei Comprehensive National Science Center,Hefei 230031,China

出　　处：《National Science Review》2022年第10期114-119,共6页国家科学评论（英文版）

基　　金：the National Key R&D Program of China(2019YFA0210004);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB36000000);the National Natural Science Foundation of China(21922509,92163105,T2122004,21905262,21890754,U2032212 and U2032160);the University Synergy Innovation Program of Anhui Province(GXXT-2020-005);the fellowship of China Postdoctoral Science Foundation(2020M682011);the Fundamental Research Funds for the Central Universities(WK2060000035).

摘　　要：Photocatalytic selective aerobic oxidation reactions are crucial in designing advanced organic intermediates,but suffer from low conversion efficiency.Hence,activating O_(2) to create suitable reactive oxygen species,such as singlet oxygen((1)^O_(2)),can significantly increase the yield of desired products.Herein,using ZnIn_(2)S_(4) nanosheets as a model system,we build a surface-modified theoretical structure,where a surface-covered non-conductive macromolecular chain,polyvinyl pyrrolidone(PVP),is bound to ZnIn_(2)S_(4) and influences the O_(2) adsorption process.PVP on the surface significantly changes the electronic structure and suppresses electron conduction of ZnIn_(2)S_(4) nanosheets.Therefore,abundantly photogenerated and long-lived species transfer their energy to physically absorbed O_(2) to efficiently generate(1)^O_(2),which can oxidize sulphides into their corresponding sulphoxides.For sulphoxidation of different sulphides,surface modification brings a 3–9-fold increase in conversion efficiency and high selectivities≥98%.This study provides a feasible way of boosting(1)^O_(2)-generation-related photocatalytic reactions.

关 键 词：surface modification long-lived species energy transfer singlet oxygen photocatalytic sulphoxidation of sulphides 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]