An investigation of the CH_(3)OH and CO selectivity of CO_(2)hydrogenation over Cu-Ce-Zr catalysts  

作　　者：Weiwei Wang Xiaoyu Zhang Min Guo Jianan Li Chong Peng 

机构地区：[1]School of Life Science and Chemistry,MinNan Science and Technology University,Quanzhou 362332,China [2]Sinochem Quanzhou Petrochemical Co.,Ltd.,Quanzhou 362100,China [3]School of Resources and Environmental Engineering,East China University of Science and Technology,Shanghai 200237,China [4]Department of Instrument Science and Engineering,School of Electronic Information and Electrical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China

出　　处：《Frontiers of Chemical Science and Engineering》2022年第6期950-962,共13页化学科学与工程前沿（英文版）

基　　金：National Natural Science Foundation of China(Grant No.22122807);Education and Scientific Research Project of Young and Middle-aged Teachers in Fujian Province(Science and Technology,JAT200979);National and Provincial College Students’Innovation and Entrepreneurship Training Plan(Grant No.202112992003);Doctoral Initiation Fund for Liaoning(Grant No.2019-BS-054);Liao Ning Revitalization Talents Program(Grant No.XLYC1807245);Natural Science Foundation of Shanghai(Grant No.21ZR1425700).

摘　　要：A series of Cu-Ce-Zr catalysts with different Ce contents are applied to the hydrogenation of CO_(2)to CO/CH3OH products.The Cu-Ce-Zr catalyst with 2 wt%Ce loading shows higher CO selectivity(S_(CO)=0.0%-87.8%)from 200-300℃,while the Cu-Ce-Zr catalyst with 8 wt%Ce loading presents higher CO_(2)conversion(X_(CO_(2))=5.4%-15.6%)and CH3OH selectivity(S_(CH_(3)OH)=97.8%-40.6%).The number of hydroxyl groups and solid solution nature play a significant role in changing the reaction pathway.The solid solution enhances the CO_(2)adsorption ability.At the CO_(2)adsorption step,a larger number of hydroxyl groups over the Cu-Ce-Zr catalyst with 8 wt%Ce loading leads to the production of H-containing adsorption species.At the CO_(2)hydrogenation step,a larger number of hydroxyl groups assists in encouraging the further hydrogenation of intermediate species to CH_(3)OH and improving the hydrogenation rate.Hence,the Cu-Ce-Zr catalyst with 8 wt%Ce loading favors CH3OH selectivity and CO_(2)activation,while CO is preferred on the Cu-Ce-Zr catalyst with 2 wt%Ce loading,a smaller number of hydroxyl groups and a solid solution nature.Additionally,high-pressure in situ diffuse reflectance infrared Fourier transform spectroscopy shows that CO is produced from formate decomposition and that both monodentate formate and bidentate formate are active intermediate species of CO_(2)hydrogenation to CH3OH.

关 键 词：CO_(2)hydrogenation Cu-Ce-Zr HYDROXYLS CO/CH3OH selectivity 

分 类 号：O643.36[理学—物理化学] O623.411[理学—化学]