文献类型：期刊文献

英文题名：Steric-confinement Rh2/MoS2 dual-atom catalyst directionally modulating adsorption configuration of ester group to boost ethanol synthesis

作者：Zhao, Yi[1,2];Gu, Qingqing[3];Sun, Xue[1,2];Wang, Dong[4,5];Gong, Xueqing[4,5];Yang, Bing[3];Xu, Jing[6];Peng, Bo[7];Zhang, Ying[1,2];Pan, Chengsi[1,2];Zhu, Yongfa[8];Lou, Yang[1,2]

机构：[1]Jiangnan Univ, Sch Chem & Mat Engn, Key Lab Synthet & Biol Colloids, Minist Educ, Wuxi 214122, Jiangsu, Peoples R China;[2]Jiangnan Univ, Int Joint Res Ctr Photorespons Mol & Mat, Wuxi 214122, Jiangsu, Peoples R China;[3]Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, 457 Zhongshan Rd, Dalian 116023, Peoples R China;[4]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[5]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[6]Jiangnan Univ, Sch Food Sci & Technol, Wuxi 214122, Jiangsu, Peoples R China;[7]SINOPEC Res Inst Petr Proc Co Ltd, Beijing 100083, Peoples R China;[8]Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China

年份：2024

卷号：10

期号：11

外文期刊名：CHEM

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001358349500001)】；

基金：This project was supported financially by the National Natural Science Foundation of China (21908079, U21A20326, 22302200, and 22273021) , National Key R&D Program of China (2021YFB3501900) , Jiangsu Specially Appointed Professor (1046010241211400) , Natural Science Foundation of Jiangsu Province (BK20211239) , Postgraduate Research and Practice Innovation Program of Jiangsu Province (nos. KYCX23_2461) , Shanghai Science and Technology Development Funds (22QA1402900) , and Dalian Institute of Chemical Physics (DICP I201943) . We also thank the Central Laboratory, School of Chemical and Material Engineering, Jiangnan University.

语种：英文

摘要：Developing a new tactic for directionally regulating a specific functional group of feedstock molecules at the molecular level is highly desired to synthesize high-value products but remains challenging. We design and construct the two-dimensional molybdenum disulfide (2D MoS2) nanosheets edge-anchored dual Rh atoms (Rh2/ MoS2 dual-atom catalyst [DAC]) to boost the ethanol yield in dimethyl oxalate (DMO) selective hydrogenation by precisely manipulating the DMO adsorption configuration. Comprehensive experimental and theoretical results reveal that the pocket-like active center of Rh2 atoms, with a precise metal-metal distance (3.5 A & ring;), realizes the spatially matched bidentate DMO adsorption via two C=O groups (distance of 3.1 A & ring;), which remarkably enhances the DMO activation and drives the production of ethanol via a unilateral activation mechanism. The turnover frequency (TOF) and H2/DMO molar ratio of Rh2/MoS2 DAC are around 19 times higher and 17 times lower, respectively, than those of the best reported catalysts under comparable conditions. Our results offer practical opportunities for updating the industrial syngas-DMO-ethanol route.