Quasi-homogeneous photoelectrochemical organic transformations for tunable products and 100%conversion ratio  

产物可调控及100%转化比率的类均相光电化学有机转化

作　　者：Cheng Lin Yuan Lu Jiaming Miao Zhongyuan Ma Youngmoon Choi Yan Yang Chaoran Dong Jinyou Shen Jong Hyeok Park Kan Zhang 林铖;陆源;缪佳明;马中原;Youngmoon Choi;杨艳;董超然;沈锦优;Jong Hyeok Park;张侃

机构地区：[1]School of Materials Science and Engineering,Nanjing University of Science and Technology,Nanjing 210094,China [2]Department of Chemical and Biomolecular Engineering,Yonsei University,Seoul 120-749,Republic of Korea [3]Key Laboratory of Environmental Remediation and Ecological Health,Ministry of Industry and Information Technology,School of Environmental and Biological Engineering,Nanjing University of Science and Technology,Nanjing 210094,China

出　　处：《Science Bulletin》2024年第21期3395-3403,共9页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China(T2322013,22172077);the Natural Science Foundation of Jiangsu Province of China(BK 20211573);the Fundamental Research Funds for the Central Universities(30921011216);C.L was supported by China Scholarship Council(CSC)(202206840088);supported by the Ministry of Science and ICT through the National Research Foundation of Korea(2022H1D3A3A01077254,2021M3H4A1A03049662);the support from Yonsei-KIST Convergence Research Program and the Yonsei Fellow Program,funded by Lee Youn Jae.

摘　　要：Photoelectrochemical(PEC)organic transformation at the anode coupled with cathodic H_(2) generation is a potentially rewarding strategy for efficient solar energy utilization.Nevertheless,achieving the full conversion of organic substrates with exceptional product selectivity remains a formidable hurdle in the context of heterogeneous catalysis at the solid/liquid interface.Here,we put forward a quasi-homogeneous catalysis concept by using the reactive oxygen species(ROS),such as·OH,H_(2)O_(2) and SO_(4)^(2-),as a charge transfer mediator instead of direct heterogeneous catalysis at the solid/liquid interface.In the context of glycerol oxidation,all ROS exhibited a preference forfirst-order reaction kinetics.These ROS,however,showcased distinct oxidation mechanisms,offering a range of advantages such as100%conversion ratios and theflexibility to tune the resulting products.Glycerol oxidative formic acid with Faradaic efficiency(FE)of 81.2%was realized by the H_(2)O_(2) and·OH,while SO_(4)^(2-)was preferably for glycerol conversion to C3 products like glyceraldehyde and dihydroxyacetone with a total FE of about 80%.Strikingly,the oxidative coupling of methane to ethanol was successfully achieved in our quasi-homogeneous system,yielding a remarkable production rate of 12.27 lmol h^(-1) and an impressive selectivity of 92.7%.This study is anticipated to pave the way for novel approaches in steering solar-driven organic conversions by manipulating ROS to attain desired products and conversion ratios.

关 键 词：Reactive oxygen species Homogeneous catalysis Photoelectrochemical organic TRANSFORMATIONS Glycerol oxidation Methane oxidation 

分 类 号：O621.251[理学—有机化学]