Mechanistic exploration of syngas conversion at the interface of graphene/Cu(111): identifying the effect of promoted electron transfer on the product selectivity

被引:5
作者
Wei, Zhongzeng [1 ]
Bai, Bing [1 ]
Bai, Hui [1 ]
Duan, Yongliang [2 ]
Yang, Mingxue [1 ]
Cao, Haojie [1 ]
Zuo, Zhijun [1 ]
Zuo, Jianping [3 ]
Wang, Qiang [4 ]
Huang, Wei [1 ]
机构
[1] Taiyuan Univ Technol, Coll Chem Engn & Technol, State Key Lab Clean & Efficient Coal Utilizat, Taiyuan 030024, Shanxi, Peoples R China
[2] Coal Chem Ind Technol Res Inst, Natl Energy Ningxia Coal Ind Grp, Yinchuan 750411, Ningxia, Peoples R China
[3] China Univ Min & Technol, Sch Mech & Civil Engn, Beijing 100083, Peoples R China
[4] Chinese Acad Sci, Inst Coal Chem, Natl Key Lab High Efficiency & Low Carbon Utilizat, Taiyuan 030001, Peoples R China
基金
中国国家自然科学基金;
关键词
CO2; HYDROGENATION; METHANOL SYNTHESIS; HIGHER ALCOHOLS; FRONTIER ORBITALS; COMBINED DFT; SURFACE; CATALYSIS; CU; COVERAGE; ETHANOL;
D O I
10.1039/d3cy01184d
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
Syngas conversion into ethanol is a promising pathway to obtain an attractive alternative fuel, but its selectivity is not ideal. Here, we used a combination of density functional theory calculations and microkinetic modeling to study the reaction mechanism of syngas conversion at the confined graphene/Cu(111) interface. It was found that the confinement using a 2D graphene cover promotes the formation of the key intermediate CH3 through H-assisted CH3O dissociation and the production of CH4, but suppresses the formation of CH3OH. Moreover, C2H5OH is the most competitive product with CH4 through CHO insertion into the easily generated CH3 species to complete the carbon chain growth. Detailed DOS and Bader charge results revealed that covering with 2D graphene promotes the electron transfer along the direction vertical to the Cu(111) surface, leads to the charge redistribution of the confined space, and eventually affects the product selectivity of syngas conversion. The corresponding degree of rate control analysis showed that the final hydrogenation step of CH3 and CH3CHOH limits the rate of the production of CH4 and C2H5OH, respectively. Furthermore, the adsorbed hydroxyl is identified as the rate controlling intermediate. Our findings provide a useful guide for further modification of Cu-based catalysts for syngas to ethanol conversion. The graphene/Cu(111) interface modulates the product selectivity of syngas conversion by promoting the electron transfer in the confined space.
引用
收藏
页码:6527 / 6540
页数:14
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