Rhodium complex-anchored and supramolecular polymer-grafted CdS nanoflower for enhanced photosynthesis of H_(2)O_(2) and photobiocatalytic C–H bond oxyfunctionalization  

作　　者：Hongwei Jia Xiaoyang Yue Yuying Hou Fei Huang Cuiyao Cao Feifei Jia Guanhua Liu Xiaobing Zheng Yunting Liu Yanjun Jiang 

机构地区：[1]School of Chemical Engineering and Technology,Hebei University of Technology,Tianjin 300401,China [2]National-Local Joint Engineering Laboratory for Energy Conversion in Chemical Process Integration and Resources Utilization,School of Chemical Engineering and Technology,Hebei University of Technology,Tianjin 300401,China

出　　处：《Frontiers of Chemical Science and Engineering》2024年第10期73-82,共10页化学科学与工程前沿（英文版）

基　　金：supported by the National Natural Science Foundation of China(Grant No.22378096);the Natural Science Foundation of Hebei Province(Grant No.B2023202014);the Science Technology Research Project of Higher Education of Hebei Province(Grant Nos.QN2021045,and QN2023207);the Tianjin Science and Technology Project(Grant No.22KPHDRC00260).

摘　　要：Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp3)–H bonds using only H_(2)O_(2) as a clean oxidant,while also exhibiting sensitivity to H_(2)O_(2) concentration.CdS-based semiconductors are promising for the photosynthesis of H_(2)O_(2) owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process,however,they suffer from fast H_(2)O_(2) decomposition on the surface of pristine CdS.Therefore,[Cp*Rh(bpy)H_(2)O]2+,a highly selective proton-coupled electron transfer catalyst,was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H_(2)O_(2),mitigating the surface issue of pristine CdS,increasing light absorption,accelerating photonic carrier separation,and enhancing oxygen reduction reaction selectivity to H_(2)O_(2).This photocatalyst promoted the light driven H_(2)O_(2) generation rate up to 1345μmol·L^(-1)·g^(-1)·h^(-1),which was 2.4 times that of pristine CdS.The constructed heterojunction photocatalyst could supply H_(2)O_(2) in situ for nonspecific peroxygenases to catalyze the C–H oxyfunctionalization of ethylbenzene,achieving a yield of 81%and an ee value of 99%under optimum conditions.A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system,achieving the corresponding chiral alcohols in good yield(51%–88%)and excellent enantioselectivity(90%–99%ee).

关 键 词：cadmium sulfide unspecific peroxygenases photobiocatalysis hydrogen peroxide OXYFUNCTIONALIZATION 

分 类 号：TQ051.893[化学工程]