Unraveling the electrophilic oxygen-mediated mechanism for alcohol electrooxidation on NiO  

作　　者：Wei Chen Jianqiao Shi Chao Xie Wang Zhou Leitao Xu Yingying Li Yandong Wu Binbin Wu Yu-Cheng Huang Bo Zhou Ming Yang Jilei Liu Chung-Li Dong Tehua Wang Yuqin Zou Shuangyin Wang 

机构地区：[1]State Key Laboratory of Chemo/Bio-Sensing and Chemometrics,College of Chemistry and Chemical Engineering,Advanced Catalytic Engineering Research Center of the Ministry of Education,Hunan University,Changsha 410082 [2]College of Chemistry and Chemical Engineering,Hunan Normal University,Changsha 410081 [3]College of Materials Science and Engineering,Hunan University,Changsha 410082 [4]Research Center for X-ray Science&Department of Physics,Tamkang University,New Taipei City 25137 [5]Shenzhen Institute of Hunan University,Shenzhen 518057

出　　处：《National Science Review》2023年第5期245-255,共11页国家科学评论（英文版）

基　　金：supported by the National Key R&D Program of China(2020YFA0710000);the National Natural Science Foundation of China(22122901,21902047,21825201 and U19A2017);the Provincial Natural Science Foundation of Hunan(2020JJ5045,2021JJ20024 and2021RC3054);the Shenzhen Science and Technology Program(JCYJ20210324140610028)。

摘　　要：Aqueous organic electrosynthesis such as nucleophile oxidation reaction(NOR)is an economical and green approach.However,its development has been hindered by the inadequate understanding of the synergy between the electrochemical and non-electrochemical steps.In this study,we unravel the NOR me chanism for the primary alcohol/vicinal diol electro oxidation on NiO.Thereinto,the ele ctrochemical step is the generation of Ni^(3+)-(OH)_(ads),and the spontaneous reaction between Ni^(3+)-(OH)_(ads)and nucle ophiles is an electrocatalyst-induced non-electrochemical step.We identify that two electrophilic oxygen-mediated mechanisms(EOMs),EOM involving hydrogen atom transfer(HAT)and EOM involving C-C bond cleavage,play pivotal roles in the electro oxidation of primary alcohol to carboxylic acid and the electrooxidation of vicinal diol to carboxylic acid and formic acid,respectively.Based on these findings,we establish a unified NOR mechanism for alcohol electrooxidation and deepen the understanding of the synergy between the electrochemical and non-electro chemical steps during NOR,which can guide the sustainable electrochemical synthesis of organic chemicals.

关 键 词：nucleophile oxidation reaction alcohol electrooxidation organic electrosynthesis nickel-based electrocatalysts C-C bond cleavage 

分 类 号：TQ031.7[化学工程]