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Engineering catalyst supports to stabilize PdOx two-dimensional rafts for water-tolerant methane oxidation

Nature Catalysis volume 4, pages 830–839 (2021)Cite this article

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Abstract

The treatment of emissions from natural gas engines is an important area of research since methane is a potent greenhouse gas. The benchmark catalysts, based on Pd, still face challenges such as water poisoning and long-term stability. Here we report an approach for catalyst synthesis that relies on the trapping of metal single atoms on the support surface, in thermally stable form, to modify the nature of further deposited metal/metal oxide. By anchoring Pt ions on a catalyst support we can tailor the morphology of the deposited phase. In particular, two-dimensional (2D) rafts of PdOx are formed, resulting in higher reaction rates and improved water tolerance during methane oxidation. The results show that modifying the support by trapping single atoms could provide an important addition to the toolkit of catalyst designers for controlling the nucleation and growth of metal and metal oxide clusters in heterogeneous catalysts.

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Fig. 1: Scanning transmission electron microscope images of 2D rafts of Pt on Pt@CeO2.
Fig. 2: CO oxidation reactivity and energetics of Pt 2D rafts deposited on the engineered catalyst support.
Fig. 3: Methane oxidation reactivity of Pd-based catalysts with and without added water vapour.
Fig. 4: AC–STEM images of atom-trapped 2Pt@CeO2 and 1Pd deposited on atom-trapped 2Pt@CeO2 (1Pd/2Pt@CeO2).
Fig. 5: XAS spectra of 1Pd/2Pt@CeO2 sample.
Fig. 6: XPS spectra of 1Pd/2Pt@CeO2 and (1Pd + 2Pt)/CeO2 catalysts.
Fig. 7: DFT simulations of methane oxidation and water dissociation over metal Pd and Pd oxides.

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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 on reasonable request. Source data are provided with this paper.

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Acknowledgements

The catalyst synthesis and characterization via transmission electron microscopy (TEM) and DRIFTS was partly supported by DOE/BES Catalysis Science program, grant no. DE-FG02-05ER15712. Reactivity measurements were supported by the US Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy under the Advanced Manufacturing Office, award number DE-LC 000L059 and from the Vehicle Technologies Office. H.X. acknowledges support from the National High-Level Young Talents programme and National Natural Science Foundation of China (grant nos. 22072118 and 2212100020). The computational work on catalysis was supported by the National Natural Science Foundation of China (grant nos. 21673040 and 21973013) and Air Force Office of Scientific Research (grant no. FA9550-18-1-0413). S.S.C. acknowledges support from the Center for Integrated Nanotechnologies (CINT), a user facility operated for the US DOE Office of Science where some of the characterization was performed. J.H. thanks National Natural Science Foundation of China (grant nos. 51772262, U20A20336 and 21935009), Natural Science Foundation of Hebei Province (grant no. B2020203037) and the Hunan Innovation Team (grant no. 2018RS3091) for financial support of this research. The characterization via XAS was supported by the National Science Foundation under Cooperative Agreement no. EEC-1647722 (CISTAR). Use of the Advanced Photon Source was supported by the US DOE Office of Basic Energy Sciences under contract no. DE-AC02-06CH11357. MRCAT operations, beamline 10-BM and 10-ID, are supported by the DOE and the MRCAT member institutions. We thank A. Genc, H. Pham and F. Shi for assistance with the TEM measurements that were performed, in part, at Thermo Fisher and at the University of Illinois at Chicago, Research Resources Center, Electron Microscopy Core. K.L. and S.S.C. acknowledge support from Sandia National Laboratories, a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the US DOE’s National Nuclear Security Administration under contract no. DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the document do not necessarily represent the views of the US DOE or the United States Government.

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Author notes

  1. These authors contributed equally: Haifeng Xiong, Deepak Kunwar, Dong Jiang.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Haifeng Xiong, Hengyu Li & Congcong Du

  2. Department of Chemical and Biological Engineering and Center for Micro-Engineered Materials, University of New Mexico, Albuquerque, NM, USA

    Deepak Kunwar, Griffin Canning & Abhaya K. Datye

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

    Dong Jiang, Carlos E. García-Vargas, Xavier Isidro Pereira-Hernandez & Yong Wang

  4. State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, China

    Qiang Wan & Sen Lin

  5. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    Stephen C. Purdy & Jeffrey T. Miller

  6. Sandia National Laboratories, Albuquerque, NM, USA

    Kevin Leung & Stanley S. Chou

  7. ION-TOF GmbH, Münster, Germany

    Hidde H. Brongersma

  8. Tascon GmbH, Münster, Germany

    Rik ter Veen

  9. Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, China

    Jianyu Huang

  10. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, NM, USA

    Hua Guo

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

    Yong Wang

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  1. Haifeng Xiong
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Contributions

S.S.C., H.X., Y.W., H.G. and A.K.D. conceived and planned the research. H.X., D.K., D.J. and H.L. synthesized the catalysts and performed catalyst characterization. DFT computations and analysis were performed by Q.W., S.L., H.G. and K.L. LEIS measurements were done by H.H.B. and R.V. H.X., D.K., C.D., J.H. and G.C. performed the TEM measurements. C.E.G.-V. and X.I.P.-H. did the DRIFTS measurements. S.C.P. and J.T.M. performed the XAS measurements. H.L. and D.J. measured the reactivity. H.X., H.G., Y.W. and A.K.D. wrote the paper. All authors discussed the results and commented on the paper.

Corresponding authors

Correspondence to Haifeng Xiong, Hua Guo, Yong Wang or Abhaya K. Datye.

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Peer review information Nature Catalysis thanks Hyunjoo Lee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–19, Tables 1–13 and References.

Supplementary Data

Pd model.

Supplementary Data

PdO raft model.

Supplementary Data

PdO particle model.

Supplementary Data 1

SourceData_for_all_XPS.

Supplementary Data 2

SourceData_Fig. S6.

Supplementary Data 3

SourceData_Fig. S7.

Supplementary Data 4

SourceData_Fig. S8.

Source data

Source Data Fig. 3

SourceData_Fig. 3.

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Xiong, H., Kunwar, D., Jiang, D. et al. Engineering catalyst supports to stabilize PdOx two-dimensional rafts for water-tolerant methane oxidation. Nat Catal 4, 830–839 (2021). https://doi.org/10.1038/s41929-021-00680-4

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