Metal-Free Ceria Catalysis for Selective Hydrogenation of Crotonaldehyde

被引：85

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

来源：

ACS CATALYSIS | 2020年 / 10卷 / 24期

关键词：

CeO2; nanocrystals; surface oxygen vacancy; frustrated Lewis pair sites; selective hydrogenation of crotonaldehyde; reaction mechanism; CHEMOSELECTIVE HYDROGENATION; DEPENDENT INTERPLAY; CARBONYL-COMPOUNDS; OXYGEN VACANCIES; CEO2; OXIDATION; REDUCTION; SUPPORT; SEMIHYDROGENATION; SPECTROSCOPY;

D O I：

10.1021/acscatal.0c04523

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

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.

引用

页码：14560 / 14566

页数：7

共 55 条

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