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Boosting CO2 hydrogenation via size-dependent metal–support interactions in cobalt/ceria-based catalysts

Nature Catalysis volume 3, pages 526–533 (2020)Cite this article

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Abstract

Metal–support interactions have a strong impact on the performance of heterogeneous catalysts. Specific sites at the metal–support interface can give rise to unusual high reactivity, and there is a growing interest in optimizing not only the properties of metal particles but also the metal–support interface. Here, we demonstrate how varying the particle size of the support (ceria–zirconia) can be used to tune the metal–support interactions, resulting in a substantially enhanced CO2 hydrogenation rate. A combination of X-ray diffraction, X-ray absorption spectroscopy, near-ambient pressure X-ray photoelectron spectroscopy, transmission electron microscopy and infrared spectroscopy provides insight into the active sites at the interface between cobalt and ceria–zirconia involved in CO2 hydrogenation to CH4. Reverse oxygen spillover from the support during treatment in hydrogen results in the generation of oxygen vacancies. Stabilization of cobalt particles by ceria–zirconia particles of intermediate size leads to oxygen spillover to the support during the CO2 and CO dissociation steps, followed by further hydrogenation of the resulting intermediates on cobalt.

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Fig. 1: The effect of support calcination pretreatment on catalytic activity.
Fig. 2: Characterization of CoCZ catalysts.
Fig. 3: The relationship between catalyst morphology and cobalt sintering.
Fig. 4: Spillover effects observed by means of operando NAP-XPS and infrared spectroscopy.

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The data that support the findings of this study are available from the authors upon reasonable request.

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Acknowledgements

This research was supported by the Applied and Engineering Sciences division of the Netherlands Organization for Scientific Research through the Alliander (now Qirion) perspective programme on Plasma Conversion of CO2. We acknowledge Diamond Light Source for time on beamline B18 under proposal SP20715-1.

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Authors and Affiliations

  1. Inorganic Materials and Catalysis Group, Eindhoven University of Technology, Eindhoven, The Netherlands

    Alexander Parastaev, Valery Muravev, Elisabet Huertas Osta, Arno J. F. van Hoof, Tobias F. Kimpel, Nikolay Kosinov & Emiel J. M. Hensen

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Contributions

A.P. synthesized and characterized the set of CZ samples (TPR, X-ray diffraction, and CO chemisorption and infrared spectroscopy). E.H.O. performed the catalytic measurements. V.M. and A.P. performed the operando NAP-XPS experiments and interpreted the results. N.K., V.M. and A.P. performed and interpreted the operando X-ray absorption spectroscopy measurements. A.J.F.H. performed the TEM measurements with an in situ holder. T.F.K. synthesized and provided the cobalt–titania sample. A.P., N.K. and E.J.M.H. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Emiel J. M. Hensen.

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Parastaev, A., Muravev, V., Huertas Osta, E. et al. Boosting CO2 hydrogenation via size-dependent metal–support interactions in cobalt/ceria-based catalysts. Nat Catal 3, 526–533 (2020). https://doi.org/10.1038/s41929-020-0459-4

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