文献类型：期刊文献

英文题名：Urchin-like Nb2O5 hollow microspheres enabling efficient and selective photocatalytic C-C bond cleavage in lignin models under ambient conditions

作者：Chen, Huan[1];Hong, Donghui[1];Wan, Kun[1];Wang, Junjie[1];Niu, Bo[1];Zhang, Yayun[1];Long, Donghui[1,2]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Shanghai Key Lab Multiphase Mat Chem Engn, Shanghai 200237, Peoples R China

年份：2022

卷号：33

期号：9

起止页码：4357

外文期刊名：CHINESE CHEMICAL LETTERS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000815137000042)】；

基金：This work was financially supported by the National Natural Science Foundation of China (No. 22008073), and Shanghai Sailing Program (No. 20YF1410600). We want to thank Profs. Dongfang Niu and Yaqiao Liu for photoelectrochemical performance (PEC) measurement, Jianlei Yao for GC support, and Hongyu Zhang for picture drawing.

语种：英文

外文关键词：Niobium oxide; Urchin-like hierarchical structure; Photocatalysis; beta-O-4 Lignin model; C-beta radical

摘要：Selective cleavage of robust C-C bonds to harvest value-added aromatic oxygenates is an intriguing but challenging task in lignin depolymerization. Photocatalysis is a promising technology with the advan- tages of mild reaction conditions and strong sustainability. Herein, we show a novel urchin-like Nb2O5 hollow microsphere (U-Nb2O5 HM), prepared by one-pot hydrothermal method, are highly active and selective for C-alpha-C-beta bond cleavage of lignin beta-O-4 model compounds under mild conditions, achieving 94% substrate conversion and 96% C-C bond cleavage selectivity. Systematic experimental studies and den- sity functional theory (DFT) calculations revealed that the superior performance of U-Nb2O5 HMs arises from more exposed active sites, more efficient free charge separation and the active (001) facet, which facilitates the activation of C-beta-H bond of lignin models and generate key C-beta radical intermediates by photogenerated holes, further inducing the C-alpha-C-beta bond cleavage to produce aromatic oxygenates. This work could provide some suggestions for the fabrication of hierarchical photocatalysts in the lignin de- polymerization system. (C) 2022 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.