文献类型：期刊文献

英文题名：Metal-Free Ceria Catalysis for Selective Hydrogenation of Crotonaldehyde

作者：Zhang, Zhenhua[1];Wang, Zhi-Qiang[1];Li, Zhaorui[2,3];Zheng, Wan-Bin[1];Fan, Liping[1];Zhang, Jing[1];Hu, Yi-Ming[1];Luo, Meng-Fei[1];Wu, Xin-Ping[4,5];Gong, Xue-Qing[4,5];Huang, Weixin[2,3,6];Lu, Ji-Qing[1]

机构：[1]Zhejiang Normal Univ, Inst Phys Chem, Zhejiang Key Lab React Chem Solid Surfaces, Key Lab,Minist Educ Adv Catalysis Mat, Jinhua 321004, Zhejiang, Peoples R China;[2]Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, Key Lab Surface & Interface Chem & Energy Catalys, CAS Key Lab Mat Energy Convers, Hefei 230026, Peoples R China;[3]Univ Sci & Technol China, Dept Chem Phys, Hefei 230026, Peoples R China;[4]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[5]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[6]Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China

年份：2020

卷号：10

期号：24

起止页码：14560

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20205209668081);WOS:【SCI-EXPANDED(收录号:WOS:000608850500017)】；

基金：The work was financially supported by the Experimental Technology Development Project of Zhejiang Normal University (No. 20200024), the Natural Science Foundation of Zhejiang Province (No. LQ20B030007), the Natural Science Foundation of China (Nos. 21773212, 21525313, 91745202, and 91945301), the Chinese Academy of Sciences, and the Changjiang Scholars Program of the Ministry of Education of China.

语种：英文

外文关键词：CeO2 nanocrystals; surface oxygen vacancy; frustrated Lewis pair sites; selective hydrogenation of crotonaldehyde; reaction mechanism

摘要：Selective hydrogenation of alpha,beta-unsaturated aldehydes to unsaturated alcohols is important for the synthesis of fine chemicals, yet very challenging. Herein, we reported a metal-free CeO2 nanorods (rCeO(2)) catalyst for gas-phase transformation of crotonaldehyde to crotyl alcohol with the highest selectivity of 93.2% at 323 K. Compared to CeO2 nanocubes and nanopolydra, r-CeO2 shows a much higher crotyl alcohol production rate, comparable turnover frequency to those of noble-metalbased catalysts, and very high crotyl alcohol selectivity. This can be associated with a relatively high density of surface oxygen vacancies on rCeO(2), which constructs the solid frustrated Lewis pair sites with enhanced heterolytic H-2 dissociation and preferred crotonaldehyde adsorption via the C=O bond. However, a further reduction of r-CeO2 by H-2 was observed to be unfavorable with regard to both catalytic activity and selectivity, because of the emergence of crotonaldehyde adsorption via the C=C bond. These findings provide a potential approach to fabricate high-performance and low-cost catalysts for selective hydrogenation of alpha,beta-unsaturated aldehydes to unsaturated alcohols using bare CeO2 with a rigid surface structure design.