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

Cu-based catalysts are highly attractive for CO<inf>2</inf> 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 ser...

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Bibliographic Details
Authors: Lu, Xuan, Garcia, Xènia, Serrano, Isabel, Biset-Peiró, Martí, Yu, Jing, Li, Junshan, Arbiol, Jordi, Cabot, Andreu, Llorca, Jordi
Format: article
Status:Published version
Publication Date:2025
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/399251
Online Access:http://hdl.handle.net/10261/399251
https://api.elsevier.com/content/abstract/scopus_id/105008697067
Access Level:Open access
Keyword:Ce0.9Zr0.1O2
CO2 hydrogenation
Cu-Ga
DRIFTS
Methanol
Description
Summary:Cu-based catalysts are highly attractive for CO<inf>2</inf> 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 Ce<inf>0.9</inf>Zr<inf>0.1</inf>O<inf>2</inf> for CO<inf>2</inf>-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 CO<inf>2</inf> adsorption and activation are favored by the appropriate Cu/Ga ratio, while Ga sites, in addition to Cu, play a critical role in promoting H<inf>2</inf> dissociation under methanol synthesis conditions. Furthermore, the oxygen vacancies in the CuGa/Ce<inf>0.9</inf>Zr<inf>0.1</inf>O<inf>2</inf> 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 CO<inf>2</inf> activation and hydrogenation steps, emphasizing Ga as an active site alongside Cu and highlighting the catalyst's potential for efficient methanol production from CO<inf>2</inf>.