A high dispersion of the active metal phase of transition metals on oxide supports is important when designing efficient heterogeneous catalysts. Besides nanoparticles, clusters and even single metal atoms can be attractive for a wide range of reactions. However, many industrially relevant catalytic transformations suffer from structure sensitivity, where reducing the size of the metal particles below a certain size substantially lowers catalytic performance. A case in point is the low activity of small cobalt nanoparticles in the hydrogenation of CO and CO2. Here we show how engineering of catalytic sites at the metal–oxide interface in cerium oxide–zirconium dioxide (ceria–zirconia)-supported cobalt can overcome this structure sensitivity. Few-atom cobalt clusters dispersed on 3 nm cobalt(II)-oxide particles stabilized by ceria–zirconia yielded a highly active CO2 methanation catalyst with a specific activity higher than that of larger particles under the same conditions.
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All data are available from the corresponding author upon reasonable request. Coordinates of optimized structures used for DFT modelling are contained in Supplementary Data 1.
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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 no. SP20715-1. This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 823717 – ESTEEM3. S.B. acknowledges support from the European Research Council (ERC Consolidator Grant no. 815128 REALNANO) and T.A. acknowledges funding from the University of Antwerp Research fund (BOF). A.B. received funding from the European Union under grant agreement no. 823717 – ESTEEM3. The authors acknowledge funding through the Hercules grant (FWO, University of Antwerp) no. I003218N, ‘Infrastructure for imaging nanoscale processes in gas/vapour or liquid environments’. I.V.K., D.B.B. and E.V.P. acknowledge the Russian Ministry of Science and Higher Education (contract no. 075-15-2021-580) for financial support with parahydrogen-based studies. Experiments using synchrotron radiation XPS were performed at the CIRCE beamline at ALBA Synchrotron with the collaboration of ALBA staff. F. Oropeza Palacio and R. C. J. van de Poll are acknowledged for help with RPES measurements.
The authors declare no competing interests.
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Supplementary Figs. 1–88, Notes 1–12, Tables 1–11, equation 1 and references.
Coordinates of optimized structures used for DFT modelling.
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Parastaev, A., Muravev, V., Osta, E.H. et al. Breaking structure sensitivity in CO2 hydrogenation by tuning metal–oxide interfaces in supported cobalt nanoparticles. Nat Catal 5, 1051–1060 (2022). https://doi.org/10.1038/s41929-022-00874-4