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Dynamic and reversible transformations of subnanometre-sized palladium on ceria for efficient methane removal

Nature Catalysis volume 6, pages 618–627 (2023)Cite this article

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Abstract

Reversibly adjusting the active structures of supported metal catalysts in response to dynamic working conditions has long been pursued. Here we report the reaction-environment-modulated transformations of subnanometre-sized Pd on CeO2 for efficient methane removal, leveraging the reaction environments at different stages of automotive exhaust aftertreatment. During the cold start of vehicles, inactive Pd1 single atoms are readily transformed into PdOx subnanometre clusters by CO even at room temperature with excess O2, resulting in boosted low-temperature CH4 oxidation. At elevated temperatures, dispersion of PdOx cluster into Pd1 against metal sintering renders outstanding hydrothermal stability to the catalyst, to be activated during the next vehicle start. Combined experimental and computational studies elucidate the dynamically evolved Pd speciation on CeO2 at an atomic level. Modulating the reversible nature of supported metals helps overcome the long-existing trade-off between low-temperature activity and high-temperature stability, also providing a new paradigm for designing intelligent catalysts that brings single-atom/cluster catalysts closer to real applications.

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Fig. 1: Performance and microscopic characterization of single-atom Pd1/CeO2 catalyst.
Fig. 2: Performance and in situ characterization of single-atom Pd1/CeO2.
Fig. 3: Performance and XAS investigation of single-atom Pd1/CeO2.
Fig. 4: Simulated Pd/CeO2 interfacial evolution in response to reaction conditions.

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Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its supplementary information files or from the corresponding authors upon reasonable request. All optimized structure and corresponding energetics of DFT calculations have been uploaded to the open data base catalysis-hub.org62 via the link https://www.catalysis-hub.org/publications/JiangDynamic2023. Source data are provided with this paper.

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Acknowledgements

This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences (SC), Division of Chemical Sciences (grant DE-FG02-05ER15712). C.E.G. and G.W. acknowledge additional support from the US DOE, Office of Energy Efficiency and Renewable Energy, Vehicle Technology Office. G.W. acknowledges the inspiration and support of A. Majumdar and P. A. Pianetta. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US DOE Office of Science by Argonne National Laboratory and was supported by the US DOE under contract DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. F.A.P. and J.H.S acknowledge support from the US DOE, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis as well as a postdoctoral fellowship from the Knut and Alice Wallenberg Foundation (grant 2019.0586). Use of Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US DOE, Office of Science, Office of Basic Energy Sciences under contract DE-AC02-76SF00515. Computational support is acknowledged from the National Energy Research Scientific Computing Center (computer time allocation m2997), a DOE Office of Science User Facility supported by the Office of Science of the US DOE under contract DE-AC02-05CH11231. The authors also acknowledge W. Huang, A. Hoffman and A. Cho for their valuable discussion on data analysis, and M. H. Engelhard for the help with X-ray photoelectron spectroscopy measurements.

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Author notes

  1. These authors contributed equally: Dong Jiang, Gang Wan, Joakim Halldin Stenlid.

Authors and Affiliations

  1. The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA, USA

    Dong Jiang, Carlos E. García-Vargas, Jianghao Zhang, Junrui Li & Yong Wang

  2. SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Gang Wan & Christopher J. Tassone

  3. Department of Mechanical Engineering, Stanford University, Stanford, CA, USA

    Gang Wan

  4. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Joakim Halldin Stenlid

  5. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Joakim Halldin Stenlid & Frank Abild-Pedersen

  6. Advanced Photon Source, Argonne National Laboratory, Lemont, IL, USA

    Chengjun Sun

  7. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, WA, USA

    Yong Wang

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Contributions

D.J., G.W., C.J.T., F.A.-P. and Y.W. conceived the research. G.W., C.S. and C.J.T. performed XAS studies. J.H.S. and F.A.-P. performed DFT computation. D.J. and Y.W. planned and supervised the rest of the experimental work. C.E.G.-V. performed AC-STEM and part of catalytic measurements. J.L. performed TEM measurements. J.Z. performed XRD measurements. D.J. synthesized the catalysts and performed catalytic and other analytical measurements. D.J., G.W., J.H.S., C.J.T., F.A.-P. and Y.W. wrote the paper. G.W. and J.H.S. contributed to polishing the paper. All authors discussed the results and commented on the paper.

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Correspondence to Dong Jiang, Frank Abild-Pedersen, Christopher J. Tassone or Yong Wang.

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Nature Catalysis thanks Andrey A. Saraev, Ivo Filot and the other, anonymous, reviewers for their contribution to the peer review of this work.

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Supplementary Information

Supplementary methods, Notes 1–5, Figs. 1–30, Tables 1–8 and References 1–48.

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Jiang, D., Wan, G., Halldin Stenlid, J. et al. Dynamic and reversible transformations of subnanometre-sized palladium on ceria for efficient methane removal. Nat Catal 6, 618–627 (2023). https://doi.org/10.1038/s41929-023-00983-8

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