Shape-dependent CO2 hydrogenation to methanol over Cu2O nanocubes supported on ZnO

The hydrogenation of CO2 to methanol over Cu/ZnO-based catalysts is highly sensitive to the surface composition and catalyst structure. Thus, its optimization requires a deep understanding of the influence of the pre-catalyst structure on its evolution under realistic reaction conditions, including...

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Detalles Bibliográficos
Autores: Kordus, David, Jelic, Jelena, Lopez Luna, Mauricio, Jiménez Divins, Nuria|||0000-0001-6010-5419, Timoshenko, Janis, Chee, See Wee, Rettenmaier, Clara, Kröhnert, Jutta, Kühl, Stefanie, Trunschke, Annette, Schlögl, Robert, Studt, Felix, Roldan Cuenya, Beatriz
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universitat Politècnica de Catalunya (UPC)
Repositorio:UPCommons. Portal del coneixement obert de la UPC
Idioma:inglés
OAI Identifier:oai:upcommons.upc.edu:2117/393804
Acceso en línea:https://hdl.handle.net/2117/393804
https://dx.doi.org/10.1021/jacs.2c11540
Access Level:acceso abierto
Palabra clave:Catalysts
Alcohols
Nanoparticles
Oxides
Transfer reactions
Catalitzadors
Nanopartícules
Òxids
Àrees temàtiques de la UPC::Enginyeria química
Descripción
Sumario:The hydrogenation of CO2 to methanol over Cu/ZnO-based catalysts is highly sensitive to the surface composition and catalyst structure. Thus, its optimization requires a deep understanding of the influence of the pre-catalyst structure on its evolution under realistic reaction conditions, including the formation and stabilization of the most active sites. Here, the role of the pre-catalyst shape (cubic vs spherical) in the activity and selectivity of ZnO-supported Cu nanoparticles was investigated during methanol synthesis. A combination of ex situ, in situ, and operando microscopy, spectroscopy, and diffraction methods revealed drastic changes in the morphology and composition of the shaped pre-catalysts under reaction conditions. In particular, the rounding of the cubes and partial loss of the (100) facets were observed, although such motifs remained in smaller domains. Nonetheless, the initial pre-catalyst structure was found to strongly affect its subsequent transformation in the course of the CO2 hydrogenation reaction and activity/selectivity trends. In particular, the cubic Cu particles displayed an increased activity for methanol production, although at the cost of a slightly reduced selectivity when compared to similarly sized spherical particles. These findings were rationalized with the help of density functional theory calculations.