Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation

2020/11/13 by Congyi Wu, Lili Lin, Jinjia Liu +14 · 2 citations
Chemical Engineering · Materials Science · #Carbon dioxide utilization in catalysis #Catalysts for Methane Reforming #Catalytic Processes in Materials Science

paper · pdf · doi:10.1038/s41467-020-19634-8

openalex publication_date 2020/11/13 · openalex created_date 2020/11/23 · openalex updated_date 2026/08/01

Abstract

Abstract Enhancing the intrinsic activity and space time yield of Cu based heterogeneous methanol synthesis catalysts through CO 2 hydrogenation is one of the major topics in CO 2 conversion into value-added liquid fuels and chemicals. Here we report inverse ZrO 2 /Cu catalysts with a tunable Zr/Cu ratio have been prepared via an oxalate co-precipitation method, showing excellent performance for CO 2 hydrogenation to methanol. Under optimal condition, the catalyst composed by 10% of ZrO 2 supported over 90% of Cu exhibits the highest mass-specific methanol formation rate of 524 g MeOH kg cat −1 h −1 at 220 °C, 3.3 times higher than the activity of traditional Cu/ZrO 2 catalysts (159 g MeOH kg cat −1 h −1 ). In situ XRD-PDF, XAFS and AP-XPS structural studies reveal that the inverse ZrO 2 /Cu catalysts are composed of islands of partially reduced 1–2 nm amorphous ZrO 2 supported over metallic Cu particles. The ZrO 2 islands are highly active for the CO 2 activation. Meanwhile, an intermediate of formate adsorbed on the Cu at 1350 cm −1 is discovered by the in situ DRIFTS. This formate intermediate exhibits fast hydrogenation conversion to methoxy. The activation of CO 2 and hydrogenation of all the surface oxygenate intermediates are significantly accelerated over the inverse ZrO 2 /Cu configuration, accounting for the excellent methanol formation activity observed.

Citations

• Projector augmented-wave method
• Generalized Gradient Approximation Made Simple
• Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set
• A consistent and accurateab initioparametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
• Effect of the damping function in dispersion corrected density functional theory
• Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2Hydrogenation Processes

Cited by

• The role of Cu1–O3 species in single-atom Cu/ZrO2 catalyst for CO2 hydrogenation
• Interpretable machine learned predictions of adsorption energies at the metal--oxide interface

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