Cerium coordination-dependent surface intermediates regulate activity in dimethyl carbonate synthesis from CO2 and methanol

被引:28
作者
Tian, Linyuan [1 ]
Tan, Zicong [1 ]
Wang, Quan [1 ]
Liao, Yin -Song [2 ]
Chou, Jyh-Pin [3 ]
Wu, Jyh-Ming [2 ]
Liu, Guoliang [4 ]
Peng, Yung-Kang [1 ,5 ]
机构
[1] City Univ Hong Kong, Dept Chem, Hong Kong, Peoples R China
[2] Natl Tsing Hua Univ, Dept Mat Sci & Engn, Hsinchu 300, Taiwan
[3] Natl Changhua Univ Educ, Dept & Grad Inst Phys, Changhua 500, Taiwan
[4] Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Peoples R China
[5] City Univ Hong Kong, Shenzhen Res Inst, Shenzhen 518057, Peoples R China
来源
APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY | 2023年 / 336卷
关键词
Dimethyl carbonate; Coordination structure; Surface methoxy species; Structure -activity relation; CeO2; ELASTIC BAND METHOD; CEO2; CATALYST; DIOXIDE; CONVERSION; TRANSESTERIFICATION; 2-CYANOPYRIDINE; NANOCRYSTALS; STABILITY; GLYCEROL;
D O I
10.1016/j.apcatb.2023.122914
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
The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol is a potential green alternative to the current industrial methods using toxic chemicals. Although many CeO2-based catalysts have been explored, the key structural factor affecting their DMC activity is still unclear. Herein, single-crystalline CeO2 catalysts bearing distinct but well-defined Ce coordination structures were examined. We found that methanol is the key species being activated by surface Ce sites (cf. CO2) to produce methyl carbonate (MC) and later DMC. The reactivity of surface methoxy species towards CO2 varies considerably with its configuration determined by Ce coordination structures. The head-to-head terminal methoxy species converts CO2 to MC faster than its atilt counterparts, resulting in a higher DMC activity. The bridging methoxy species is, however, too stable to react with CO2. The established structure-activity relation here should also guide the design of CeO2-based catalysts in other reactions involving methanol activation.
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页数:10
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