文献类型：期刊文献

英文题名：Hydrogenolysis Cleavage of the Csp2-Csp3 Bond over a Metal-Free NbOPO4 Catalyst

作者：Zhou, Hao[1];Chen, Lu[2,3,4];Guo, Yong[1];Liu, Xiaohui[1];Wu, Xin-Ping[2,3,4];Gong, Xue-Qing[2,3,4];Wang, Yanqin[1]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Res Inst Ind Catalysis, Shanghai Key Lab Funct Mat Chem, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Ctr Computat Chem, Feringa Nobel Prize Scientist Joint Res Ctr, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Ctr Computat Chem, Feringa Nobel Prize Scientist Joint Res Ctr, Joint Int Res Lab Precis Chem & Mol Engn, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2022

卷号：12

期号：9

起止页码：4806

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20221712034280);WOS:【SCI-EXPANDED(收录号:WOS:000813324700001)】；

基金：This work was supported financially by the NSFC of China (nos. 21832002, 21808063, 21808043, 21872050, 22003016, 92145302) and the Science and Technology Commission of Shanghai Municipality (10dz2220500).

语种：英文

外文关键词：hydrogenolysis; lignin model compound; plastic; metal free catalyst; activation and cleavage of H-2

摘要：Ru/NbOx catalysts, which combine the merits of facile hydrogen activation, a strong binding ability to the benzene ring, and the presence of Bronsted acid sites, were well investigated toward C-sp2-C-sp3 bond cleavage in the utilization of lignin and aromatic plastics (Chem 2019, 5, 1521; Angew. Chem. Int. Ed. 2021, 60, 5527). Herein, we unlock the ability of a bare NbOx catalyst in the dissociation and activation of a hydrogen molecule and further hydrogenolysis of the robust C-sp2-C-sp3 model compounds. In situ diffuse reflectance infrared Fourier transform and density functional theory calculations reveal that H-2 can be dissociated and the stable surface hydride species can be produced over Nb2O5 through heterolytic and homolytic cleavages of H-2 due to the existence of surface oxygen vacancies. Furthermore, the NbOPO4 catalyst with rich oxygen vacancy and Bronsted acidity not only allows the conversion of phenylcyclohexane to monocyclic compounds but also enables the conversion of polystyrene to arenes with a high selectivity by cleaving the C-sp2-C-sp3 bond. This study provides and proves the unique ability of the NbOPO4 catalyst in heterolytic and homolytic cleavages of H-2 and the hydrogenolysis of robust C-sp2-C-sp3 bond containing compounds, including plastics, which would help to design low-cost metal-free hydrogenolysis catalysts.