Zr(IV) surface sites determine CH3OH formation rate on Cu/ZrO2/SiO2-CO2 hydrogenation catalysts

doi:10.1016/S1872-2067(19)63348-6

Chinese Journal of Catalysis ›› 2019, Vol. 40 ›› Issue (11): 1741-1748.DOI: 10.1016/S1872-2067(19)63348-6

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Zr(IV) surface sites determine CH₃OH formation rate on Cu/ZrO₂/SiO₂-CO₂ hydrogenation catalysts

Erwin Lam^a, Kim Larmier^a,c, Shohei Tada^a,d, Patrick Wolf^a, Olga V. Safonova^b, Christophe Copéret^a

a ETH Zürich, Department of Chemistry and Applied Biosciences, Vladimir-Prelog-Weg 1-5, CH 8093, Zürich, Switzerland;
b Paul Scherrer Institute, CH-5232 Villigen, Switzerland;
c IFP Energies Nouvelles, Rond-Point de l'échangeur de Solaize, BP3, 69360 Solaize, France;
d Department of Chemical System Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656 Tokyo, Japan

Received:2019-01-12 Revised:2019-03-05 Online:2019-11-18 Published:2019-09-06
Contact: Christophe Copéret
Supported by:
E.L., K.L., P.W., and S.T. are supported by the SCCER-Heat and Energy Storage program. We acknowledge PSI Super-XAS for beamtime and thank Dr. Maarten Nachtegaal (PSI) for assistance and ScopeM at ETH Zürich for the use of their electron microscopy facilities and Dr. Dmitry Lebedev (ETH) for TEM.

Abstract

Abstract: Cu/ZrO₂/SiO₂ are efficient catalysts for the selective hydrogenation of CO₂ to CH₃OH. In order to understand the role of ZrO₂ in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO₂, 2) coordinatively saturated and 3) unsaturated Zr(IV) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH₃OH formation rates, thus indicating the importance of Zr(IV) Lewis acid surface sites in driving the selectivity toward CH₃OH. This finding is consistent with the proposed mechanism, where CO₂ is hydrogenated at the interface between the Cu nanoparticles that split H₂ and Zr(IV) surface sites that stabilizes reaction intermediates.

Key words: CO₂ hydrogenation, ZrO₂/SiO₂ supported Cu nanoparticles, Lewis acidic surface sites, In situ X-ray absorption spectroscopy

Erwin Lam, Kim Larmier, Shohei Tada, Patrick Wolf, Olga V. Safonova, Christophe Copéret. Zr(IV) surface sites determine CH₃OH formation rate on Cu/ZrO₂/SiO₂-CO₂ hydrogenation catalysts[J]. Chinese Journal of Catalysis, 2019, 40(11): 1741-1748.

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Zr(IV) surface sites determine CH₃OH formation rate on Cu/ZrO₂/SiO₂-CO₂ hydrogenation catalysts

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