Low-nuclearity CuZn ensembles on ZnZrOx catalyze methanol synthesis from CO2

Thaylan Pinheiro Araújo, Georgios Giannakakis, Jordi Morales-Vidal, Mikhail Agrachev, Zaira Ruiz-Bernal, Phil Preikschas, Tangsheng Zou, Frank Krumeich, Patrik O. Willi, Wendelin J. Stark, Robert N. Grass, Gunnar Jeschke, Sharon Mitchell, Núria López and Javier Pérez-Ramírez ()
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Thaylan Pinheiro Araújo: Department of Chemistry and Applied Biosciences
Georgios Giannakakis: Department of Chemistry and Applied Biosciences
Jordi Morales-Vidal: The Barcelona Institute of Science and Technology
Mikhail Agrachev: Department of Chemistry and Applied Biosciences
Zaira Ruiz-Bernal: University of Alicante
Phil Preikschas: Department of Chemistry and Applied Biosciences
Tangsheng Zou: Department of Chemistry and Applied Biosciences
Frank Krumeich: Department of Chemistry and Applied Biosciences
Patrik O. Willi: Department of Chemistry and Applied Biosciences
Wendelin J. Stark: Department of Chemistry and Applied Biosciences
Robert N. Grass: Department of Chemistry and Applied Biosciences
Gunnar Jeschke: Department of Chemistry and Applied Biosciences
Sharon Mitchell: Department of Chemistry and Applied Biosciences
Núria López: The Barcelona Institute of Science and Technology
Javier Pérez-Ramírez: Department of Chemistry and Applied Biosciences

Nature Communications, 2024, vol. 15, issue 1, 1-15

Abstract: Abstract Metal promotion could unlock high performance in zinc-zirconium catalysts, ZnZrOx, for CO2 hydrogenation to methanol. Still, with most efforts devoted to costly palladium, the optimal metal choice and necessary atomic-level architecture remain unclear. Herein, we investigate the promotion of ZnZrOx catalysts with small amounts (0.5 mol%) of diverse hydrogenation metals (Re, Co, Au, Ni, Rh, Ag, Ir, Ru, Pt, Pd, and Cu) prepared via a standardized flame spray pyrolysis approach. Cu emerges as the most effective promoter, doubling methanol productivity. Operando X-ray absorption, infrared, and electron paramagnetic resonance spectroscopic analyses and density functional theory simulations reveal that Cu0 species form Zn-rich low-nuclearity CuZn clusters on the ZrO2 surface during reaction, which correlates with the generation of oxygen vacancies in their vicinity. Mechanistic studies demonstrate that this catalytic ensemble promotes the rapid hydrogenation of intermediate formate into methanol while effectively suppressing CO production, showcasing the potential of low-nuclearity metal ensembles in CO2-based methanol synthesis.

Date: 2024
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DOI: 10.1038/s41467-024-47447-6

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