Identification of the dehydration active sites in glycerol hydrogenolysis to 1,2-propanediol over Cu/SiO2 catalysts

被引:49
作者
Shan, Jianfeng [1 ,2 ,3 ]
Liu, Huan [1 ,3 ]
Lu, Kuan [1 ,3 ,4 ]
Zhu, Shanhui [1 ]
Li, Junfen [1 ]
Wang, Jianguo [1 ,3 ]
Fan, Weibin [1 ]
机构
[1] Chinese Acad Sci, Inst Coal Chem, State Key Lab Coal Convers, 27 South Taoyuan Rd, Taiyuan 030001, Peoples R China
[2] Shandong Agr Univ, Coll Chem & Mat Sci, 61 Daizong Rd, Tai An 271018, Shandong, Peoples R China
[3] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
[4] Synfuels China Co, Natl Energy Ctr Coal Clean Fuels, Beijing 101400, Peoples R China
基金
中国国家自然科学基金;
关键词
Glycerol; Hydrogenolysis; 1,2-Propanediol; Cu/SBA-15; Interface; TOTAL-ENERGY CALCULATIONS; SELECTIVE HYDROGENOLYSIS; DIMETHYL OXALATE; PERFORMANCE; HYDROGENATION; EFFICIENT; SBA-15; METHANOL; ACID; FUNCTIONALIZATION;
D O I
10.1016/j.jcat.2019.12.032
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
Metal-support interaction is a hot topic in catalysis, but attention has seldom been drawn to the promotional effect of metal-irreducible SiO2 interfaces. Here, Cu/SBA-15 catalysts with Cu-O-Si-O- interface structures were prepared by simple grinding, and showed high activity and selectivity to 1,2-propanediol above 97% in liquid-phase glycerol hydrogenolysis. Glycerol conversion of ground Cu/SBA-15 with 10% Cu loading was about seven times that of its impregnation counterpart. The linear relationship between turnover frequency and (Cu-O-Si-O- induced Lewis acid sites)/Cu-0 ratio indicated that Cu-O-Si-O- structures were crucial for achieving excellent hydrogenolysis performance. More importantly, in situ Fourier transform infrared spectroscopy of glycerol adsorption and density functional theory calculation results confirmed that Cu-O-Si-O- species were the dominant active dehydration sites of glycerol hydrogenolysis, while the adjacent Cu sites were involved in subsequent hydrogenation of the generated hydroxyacetone. (C) 2019 Elsevier Inc. All rights reserved.
引用
收藏
页码:13 / 23
页数:11
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