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Interface dynamics of Pd–CeO2 single-atom catalysts during CO oxidation

Abstract

In recent years, noble metals atomically dispersed on solid oxide supports have become a frontier of heterogeneous catalysis. In pursuit of an ultimate atom efficiency, the stability of single-atom catalysts is pivotal. Here we compare two Pd/CeO2 single-atom catalysts that are active in low-temperature CO oxidation and display drastically different structural dynamics under the reaction conditions. These catalysts were obtained by conventional impregnation on hydrothermally synthesized CeO2 and one-step flame spray pyrolysis. The oxidized Pd atoms in the impregnated catalyst were prone to reduction and sintering during CO oxidation, whereas they remained intact on the surface of the Pd-doped CeO2 derived by flame spray pyrolysis. A detailed in situ characterization linked the stability of the Pd single atoms to the reducibility of the Pd–CeO2 interface and the extent of reverse oxygen spillover. To understand the chemical phenomena that underlie the metal–support interactions is crucial to the rational design of stable single-atom catalysts.

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Fig. 1: Structure of as-prepared ceria-supported Pd SACs.
Fig. 2: CO oxidation kinetics.
Fig. 3: Reaction-induced structural changes of the Pd sites.
Fig. 4: Pd speciation followed by in situ NAP-XPS.
Fig. 5: Redox chemistry of Pd–CeO2 interface probed by in situ spectroscopy.
Fig. 6: Schematic overview of the SACs evolution during CO oxidation revealed by in situ spectroscopy.

Data availability

The data that support the findings of this study are included in the published article (and its Supplementary Information) or available from the corresponding author upon reasonable request.

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Acknowledgements

E.J.M.H. and V.M. acknowledge support by the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), a NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands. C.E. acknowledges funding from the MICINN/FEDER RTI2018-093996-B-32 project. We thank the Diamond Light Source for time on beamline B18 under proposal SP22225. We thank the staff at the BM26A DUBBLE beamline at the ESRF (Grenoble) for the allocation of beam time under proposal 26-01-1166. We thank T. Kimpel and W. Vrijburg for help during the XAS measurements. Experiments using synchrotron radiation XPS were performed at the CIRCE beamline at ALBA Synchrotron with the collaboration of ALBA staff and CALIPSOplus (Grant 730872) funding. F. Oropeza Palacio and F. Coumans are acknowledged for the help with RPES measurements. J. Simons is acknowledged for the help with step-response experiments.

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Contributions

V.M. and G.S. synthesized and characterized (XRD, Brunauer–Emmet–Teller and ICP) the set of ceria samples. Y.-Q.S. helped with the interpretation of the results. V.M. performed the catalytic testing, in situ NAP-XPS and DRIFTS experiments. V.M. and A.P. performed the pulsing CO chemisorption and transmission infrared spectroscopy measurements. V.M. and A.L. performed the combined XAS/WAXS study at the ESRF. V.M., A.P. and C.E. performed the in situ RPES measurements. F.-K.C. performed the high-resolution transmission electron microscopy measurements and STEM–EDX mapping. V.M., A.P., N.K. and E.J.M.H. wrote the paper. All the authors discussed the results and commented on the manuscript.

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Correspondence to Emiel J. M. Hensen.

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Supplementary Figs. 1–50, Notes 1–10 and Tables 1–3.

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Muravev, V., Spezzati, G., Su, YQ. et al. Interface dynamics of Pd–CeO2 single-atom catalysts during CO oxidation. Nat Catal 4, 469–478 (2021). https://doi.org/10.1038/s41929-021-00621-1

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