Low-nuclearity CuZn ensembles on ZnZrO x catalyze methanol synthesis from CO 2 .

Autor: Pinheiro Araújo T; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Giannakakis G; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Morales-Vidal J; Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain., Agrachev M; Laboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 2, 8093, Zurich, Switzerland., Ruiz-Bernal Z; Department of Inorganic Chemistry and Materials Institute (IUMA), Faculty of Sciences, University of Alicante, Ap. 99, E-03080, Alicante, Spain., Preikschas P; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Zou T; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Krumeich F; Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Willi PO; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Stark WJ; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Grass RN; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., Jeschke G; Laboratory of Physical Chemistry, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 2, 8093, Zurich, Switzerland., Mitchell S; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland., López N; Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain., Pérez-Ramírez J; Institute of Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 1, 8093, Zurich, Switzerland. jpr@chem.ethz.ch.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2024 Apr 10; Vol. 15 (1), pp. 3101. Date of Electronic Publication: 2024 Apr 10.
DOI: 10.1038/s41467-024-47447-6
Abstrakt: Metal promotion could unlock high performance in zinc-zirconium catalysts, ZnZrO x , for CO 2 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 ZnZrO x 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 Cu 0 species form Zn-rich low-nuclearity CuZn clusters on the ZrO 2 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 CO 2 -based methanol synthesis.
(© 2024. The Author(s).)
Databáze: MEDLINE
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