Supported Cu catalysts on UiO-66 toward enhanced methanol selectivity by CO2 hydrogenation: Effect of Cu loading

被引:5
|
作者
Marcos, Francielle Candian Firmino [1 ,5 ]
Costa, Maria Jose Fonseca [2 ]
Catuzo, Gabriel L. [1 ]
de Moraes, Daniel Angeli [1 ]
de Oliveira Junior, Marcos [2 ]
Mastelaro, Valmor Roberto [2 ]
Assaf, Jose Mansur [3 ]
Giudici, Reinaldo [4 ]
Assaf, Elisabete Morreira [1 ,5 ]
机构
[1] Univ Sao Paulo, Sao Carlos Inst Chem, BR-13560970 Sao Carlos, SP, Brazil
[2] Univ Sao Paulo, Sao Carlos Inst Phys, POB 369, BR-13560970 Sao Carlos, SP, Brazil
[3] Univ Fed Sao Carlos, Dept Chem Engn, BR-13565905 Sao Carlos, SP, Brazil
[4] Univ Sao Paulo, Dept Chem Engn, Escola Politecn, BR-05508010 Sao Paulo, SP, Brazil
[5] Clemson Univ, Dept Chem & Biomol Engn, Clemson, SC 29634 USA
基金
巴西圣保罗研究基金会;
关键词
CO; 2; hydrogenation; Methanol; UiO-66; Cu NPs; METAL-ORGANIC FRAMEWORK; CARBON-DIOXIDE; RAW-MATERIAL; NANOPARTICLES; ADSORPTION; DEPENDENCE; DEFECTS; TOLUENE; SITES; ALPHA;
D O I
10.1016/j.jcat.2023.115104
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 xCu/MOF catalysts were synthesized by incipient-wetness impregnation of copper precursor on UiO-66 support, in which the Cu loadings were 5, 10, and 20% (wt.%). To gain insight into the properties of the materials, a range of techniques, including XRD, TEM, TGA, N2 physisorption, CO2-TPD, EDS, N2O chemisorption, XPS, IR, and NMR, were employed. The effectiveness of catalysts was evaluated for synthesizing methanol through CO2 hydrogenation under various Gas Hourly Space Velocities (GHSVs) and reaction conditions, including pressures of 10 and 30 bar, CO2/H2 ratios of 1:3, and CO2/H2/N2 ratios of 1:3:0.14 M, all conducted at a temperature of 250 degrees C. The active site in the Cu/UiO-66 catalyst is the interface between Cu+ nanoparticles (NPs) with Zr oxide SBU [Zr6O4(OH)4(-CO2) and the defects related to unsaturated Zr sites of the Zr-Oxo cluster due to the increase of Cu NPs occupying missing linker defects of the MOF structure. 20Cu/MOF catalyst, with the highest copper loading, showed the best methanol formation rate and CO2 conversion due to the strong metal-support interaction and the highest amount of the missing linker defects of the MOF structure.
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页数:9
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