Ab initio study of CO2 hydrogenation mechanisms on inverse ZnO/Cu catalysts
作者： Thomas Reichenbach , Krishnakanta Mondal , Marc Jäger , Thomas Vent-Schmidt , Daniel Himmel
DOI: 10.1016/J.JCAT.2018.01.035
关键词: Physical chemistry 、 Wave function 、 Chemistry 、 Methanol 、 Coupled cluster 、 Ab initio 、 Cubic zirconia 、 Density functional theory 、 Formate 、 Catalysis
摘要: Abstract Methanol formation from CO2 and molecular hydrogen on ZnO/Cu catalysts is studied by gradient corrected density functional theory. The catalytically active region modeled as a minimum size inverse catalyst represented ZnXOY(H) clusters of different ZnO nano-ribbon an extended Cu(1 1 1) surface. These systems are chosen representative thermodynamically stable structures under typical reaction conditions. Comparison to high level wave function method reveals that theory systematically underestimates barriers, but nevertheless conserves their energetic ordering. In contrast other metal-supported oxides like ceria zirconia, the proceeds through formate ZnOX/Cu, thus avoiding CO intermediate. difference between attributed variance in initial activation CO2. energetics pathway insensitive exact environment undercoordinated Zn sites, which points general mechanism for Cu-Zn based catalysts.
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