Water and Cu+ synergy in selective CO2 hydrogenation to methanol over Cu/MgO catalysts

28 December 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The CO2 hydrogenation reaction to produce methanol holds great significance as it contributes to achieving a CO2-neutral economy. Previous research identified isolated Cu+ species doping the oxide surface of a Cu-MgO-Al2O3 mixed oxide derived from a hydrotalcite precursor as the active site in CO2 hydrogenation, stabilizing monodentate formate species as a crucial intermediate in methanol synthesis. In this work, we present a molecular-level understanding of how surface water and hydroxyl groups play a crucial role in facilitating spontaneous CO2 activation at Cu+ sites and the formation of monodentate formate species. The computational evidence has been experimentally validated by comparing the catalytic performance of the Cu-MgO-Al2O3 catalyst with hydroxyl groups against its hydrophobic counterpart, where hydroxyl groups are blocked using an esterification method. Our work highlights the synergistic effect between doped Cu+ ions and adjacent hydroxyl groups, both of which serve as key parameters in regulating methanol production via CO2 hydrogenation. By elucidating the specific roles of these components, we contribute to advancing the understanding of the underlying mechanisms and provide valuable insights for optimizing methanol synthesis processes.


Computational chemistry
Heterogéneos catalysis
CO2 hydrogenation

Supplementary materials

Theoretical and experimental complementary data
Theoretical and experimental data that supports the main conclusions off the main text. Contains: Structural Cu-doped MgO(100) models. Formate adsorption structures with a varying degree of hydroxylation. H2O and CO2 adsorption and dissociation structures. H2 activation on MgO-Al2O3 and Cu-MgO-Al2O3 hydrophobic samples. H spillover structures. COOH, HCOOH, and H2COH adsorption structures. Charge density difference plots. Synthesis, characterization and catalytic performance of Cu-MgO-Al2O3 hydrophobic sample.

Supplementary weblinks


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