Cu and Ga dual sites on Ce0.9Zr0.1O2 for CO2 hydrogenation to methanol

Cu-based catalysts are highly attractive for CO2 hydrogenation to methanol due to their efficiency, selectivity, and cost-effectiveness. To further accelerate methanol synthesis, dual-site activation mechanisms are particularly effective. In this direction, solid solutions serve as effective support...

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Detalles Bibliográficos
Autores: Lu, Xuan, García de Andrés, Xènia|||0000-0003-0795-4168, Serrano Carreño, M. Isabel|||0000-0002-4996-9280, Biset Peiró, Martí, Yu, Jing, Li, Junshan, Arbiol Cobos, Jordi, Cabot, Andreu, Llorca Piqué, Jordi|||0000-0002-7447-9582
Tipo de recurso: artículo
Fecha de publicación:2025
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:2117/443075
Acceso en línea:https://hdl.handle.net/2117/443075
https://dx.doi.org/10.1016/j.jcat.2025.116295
Access Level:acceso abierto
Palabra clave:CO2 hydrogenation
Methanol
Cu-Ga
Ce0.9Zr0.1O2
DRIFTS
Àrees temàtiques de la UPC::Enginyeria química
Descripción
Sumario:Cu-based catalysts are highly attractive for CO2 hydrogenation to methanol due to their efficiency, selectivity, and cost-effectiveness. To further accelerate methanol synthesis, dual-site activation mechanisms are particularly effective. In this direction, solid solutions serve as effective supports, enhancing methanol production through improved hydrogenation, though the exact nature of the active sites in CuGa-based solid solutions remains unclear. In this study, we examine the synergistic interactions between Ga and Cu nanoparticles/clusters deposited on Ce0.9Zr0.1O2 for CO2-to-methanol hydrogenation. Through in situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed (TPR/TPD), we analyze the nature of the active sites and elucidate the reaction pathway. The results demonstrate that CO2 adsorption and activation are favored by the appropriate Cu/Ga ratio, while Ga sites, in addition to Cu, play a critical role in promoting H2 dissociation under methanol synthesis conditions. Furthermore, the oxygen vacancies in the CuGa/Ce0.9Zr0.1O2 catalyst play a crucial role in stabilizing the key *HCOO intermediate, facilitating its further hydrogenation to methanol via the formate pathway. This synergy between Ga and Cu optimizes both CO2 activation and hydrogenation steps, emphasizing Ga as an active site alongside Cu and highlighting the catalyst’s potential for efficient methanol production from CO2.