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Sinter-resistant metal nanoparticle catalysts achieved by immobilization within zeolite crystals via seed-directed growth

Nature Catalysis volume 1, pages 540–546 (2018)Cite this article

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Abstract

Supported metal nanoparticle catalysts are widely used in industry but suffer from deactivation resulting from metal sintering and coke deposition at high reaction temperatures. Here, we show an efficient and general strategy for the preparation of supported metal nanoparticle catalysts with very high resistance to sintering by fixing the metal nanoparticles (platinum, palladium, rhodium and silver) with diameters in the range of industrial catalysts (0.8–3.6 nm) within zeolite crystals (metal@zeolite) by means of a controllable seed-directed growth technique. The resulting materials are sinter resistant at 600–700 °C, and the uniform zeolite micropores allow for the diffusion of reactants enabling contact with the metal nanoparticles. The metal@zeolite catalysts exhibit long reaction lifetimes, outperforming conventional supported metal catalysts and commercial catalysts consisting of metal nanoparticles on the surfaces of solid supports during the catalytic conversion of C1 molecules, including the water-gas shift reaction, CO oxidation, oxidative reforming of methane and CO2 hydrogenation.

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Fig. 1: Schematic model of metal nanoparticles fixed within and on the outer surfaces of zeolite crystals.
Fig. 2: TEM images of supported platinum catalysts.
Fig. 3: TEM characterization of Pt@Beta.
Fig. 4: Catalytic evaluation of metal@zeolite catalysts in flow reactors.

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Acknowledgements

This work is supported by the National Key Research and Development Program of China (2018YFB060128) and National Natural Science Foundation of China (91645105, 91634201 and 21720102001). L.W. gratefully acknowledges the Natural Science Foundation of Zhejiang Province (LR18B030002). B.C.G. acknowledges financial support from the US Department of Energy, Office of Science, Basic Energy Sciences (grant DE-FG02-04ER15513). H.Z. acknowledges financial support from the Carl-Zeiss-Stiftung. The work reported in this paper is protected by Chinese patents (application numbers 201610342078.0 and 201610341082.5).

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Authors and Affiliations

  1. Key Laboratory of Applied Chemistry of Zhejiang Province, Zhejiang University, Hangzhou, China

    Jian Zhang, Liang Wang, Guoxiong Wang, Chengtao Wang & Feng-Shou Xiao

  2. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, China

    Jian Zhang & Feng-Shou Xiao

  3. Department of Chemistry, Zhejiang University, Hangzhou, China

    Jian Zhang, Liang Wang, Guoxiong Wang, Chengtao Wang & Feng-Shou Xiao

  4. Shenyang National Laboratory of Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, China

    Bingsen Zhang & Dang Sheng Su

  5. Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg University Mainz, Mainz, Germany

    Haishuang Zhao & Ute Kolb

  6. Advanced Membranes and Porous Materials Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Yihan Zhu, Lingmei Liu & Yu Han

  7. Department of Chemical Engineering, Zhejiang University of Technology, Hangzhou, China

    Yihan Zhu

  8. Department of Chemical Engineering, University of California, Davis, Davis, CA, USA

    Bruce C. Gates

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Contributions

J.Z. performed the catalyst preparation, characterizations and catalytic tests. G.W. and C.W. performed the catalytic tests. B.Z., D.S.S., H.Z., U.K., Y.Z., L.L. and Y.H. performed the TEM characterization. B.C.G. performed the data analysis and offered helpful suggestions. L.W. and F.-S.X. designed this study, analysed the data and wrote the paper.

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Correspondence to Liang Wang or Feng-Shou Xiao.

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Zhang, J., Wang, L., Zhang, B. et al. Sinter-resistant metal nanoparticle catalysts achieved by immobilization within zeolite crystals via seed-directed growth. Nat Catal 1, 540–546 (2018). https://doi.org/10.1038/s41929-018-0098-1

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