title: CO2-to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface.
abstract: Methanol synthesis by CO2hydrogenation is a key process in a methanol-based economy. This reaction is catalyzed by supported copper nanoparticles and displays strong support or promoter effects. Zirconia is known to enhance both the methanol production rate and the selectivity. Nevertheless, the origin of this observation and the reaction mechanisms associated with the conversion of CO2to methanol still remain unknown. A mechanistic study of the hydrogenation of CO2on Cu/ZrO2is presented. Using kinetics, in situ IR and NMR spectroscopies, and isotopic labeling strategies, surface intermediates evolved during CO2hydrogenation were observed at different pressures. Combined with DFT calculations, it is shown that a formate species is the reaction intermediate and that the zirconia/copper interface is crucial for the conversion of this intermediate to methanol.
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1-5, 8093, Zürich, Switzerland.
authors.forename: Kim
authors.identifier: 0000-0002-5199-1516
authors.initials: K
authors.lastname: Larmier
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1-5, 8093, Zürich, Switzerland.
authors.forename: Wei-Chih
authors.initials: WC
authors.lastname: Liao
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1-5, 8093, Zürich, Switzerland.
authors.forename: Shohei
authors.initials: S
authors.lastname: Tada
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1-5, 8093, Zürich, Switzerland.
authors.forename: Erwin
authors.identifier: 0000-0002-8641-7928
authors.initials: E
authors.lastname: Lam
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1-5, 8093, Zürich, Switzerland.
authors.forename: René
authors.initials: R
authors.lastname: Verel
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Atul
authors.initials: A
authors.lastname: Bansode
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Atsushi
authors.initials: A
authors.lastname: Urakawa
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1-5, 8093, Zürich, Switzerland.
authors.forename: Aleix
authors.identifier: 0000-0002-7002-1582
authors.initials: A
authors.lastname: Comas-Vives
authors.affiliation: Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog Weg 1-5, 8093, Zürich, Switzerland.
authors.forename: Christophe
authors.identifier: 0000-0001-9660-3890
authors.initials: C
authors.lastname: Copéret
keywords: CO2 hydrogenation; copper; density functional theory; solid-state NMR; zirconia