Enhanced CH3OH selectivity in CO2 hydrogenation using Cu-based catalysts generated via SOMC from GaIII single-sites

Erwin Lam; Gina Noh; Ka Wing Chan; Kim Larmier; Dmitry Lebedev; Keith Searles; Patrick Wolf; Olga V. Safonova; Christophe Copéret

doi:10.1039/D0SC00465K

Enhanced CH₃OH selectivity in CO₂ hydrogenation using Cu-based catalysts generated via SOMC from Ga^III single-sites†

Erwin Lam,^a Gina Noh,^a Ka Wing Chan,

^a Kim Larmier,

^a Dmitry Lebedev,

^a Keith Searles,^a Patrick Wolf,^a Olga V. Safonova

^b and Christophe Copéret

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir Prelog Weg 2, CH-8093 Zurich, Switzerland
E-mail: ccoperet@ethz.ch

^b Paul Scherrer Institute, CH-5232 Villigen, Switzerland

Abstract

Small and narrowly distributed nanoparticles of copper alloyed with gallium supported on silica containing residual Ga^III sites can be obtained via surface organometallic chemistry in a two-step process: (i) formation of isolated Ga^III surface sites on SiO₂ and (ii) subsequent grafting of a Cu^I precursor, [Cu(O^tBu)]₄, followed by a treatment under H₂ to generate CuGa_x alloys. This material is highly active and selective for CO₂ hydrogenation to CH₃OH. In situ X-ray absorption spectroscopy shows that gallium is oxidized under reaction conditions while copper remains as Cu⁰. This CuGa material only stabilizes methoxy surface species while no formate is detected according to ex situ infrared and solid-state nuclear magnetic resonance spectroscopy.

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DOI: https://doi.org/10.1039/D0SC00465K
Article type: Edge Article
Submitted: 24 Jan 2020
Accepted: 25 Feb 2020
First published: 26 Feb 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2020,11, 7593-7598

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Enhanced CH₃OH selectivity in CO₂ hydrogenation using Cu-based catalysts generated via SOMC from Ga^III single-sites

E. Lam, G. Noh, K. W. Chan, K. Larmier, D. Lebedev, K. Searles, P. Wolf, O. V. Safonova and C. Copéret, Chem. Sci., 2020, 11, 7593 DOI: 10.1039/D0SC00465K

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