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Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis

Nature Materials volume 18, pages 866–873 (2019)Cite this article

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Abstract

Subnanometric metal species (single atoms and clusters) have been demonstrated to be unique compared with their nanoparticulate counterparts. However, the poor stabilization of subnanometric metal species towards sintering at high temperature (>500 °C) under oxidative or reductive reaction conditions limits their catalytic application. Zeolites can serve as an ideal support to stabilize subnanometric metal catalysts, but it is challenging to localize subnanometric metal species on specific sites and modulate their reactivity. We have achieved a very high preference for localization of highly stable subnanometric Pt and PtSn clusters in the sinusoidal channels of purely siliceous MFI zeolite, as revealed by atomically resolved electron microscopy combining high-angle annular dark-field and integrated differential phase contrast imaging techniques. These catalysts show very high stability, selectivity and activity for the industrially important dehydrogenation of propane to form propylene. This stabilization strategy could be extended to other crystalline porous materials.

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Fig. 1: One-pot synthesis of Pt-zeolite materials.
Fig. 2: Characterization of Pt-zeolite materials by X-ray absorption spectroscopy.
Fig. 3: Identification of the location of subnanometric Pt clusters within the MFI structure.
Fig. 4: Chemical analysis of the K-PtSn@MFI sample.
Fig. 5: Catalytic performance of Pt-zeolite materials for propane dehydrogenation reaction.

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All the data reported in this paper are available from the corresponding author on request.

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Acknowledgements

This work has been supported by the European Union through the European Research Council (grant ERC-AdG-2014-671093, SynCatMatch) and the Spanish government through the Severo Ochoa Programme (SEV-2016-0683). L.L. thanks ITQ for providing a contract. The authors also thank the Microscopy Service of UPV for the TEM and STEM measurements. The XAS measurements were carried out in CLAESS beamline at the ALBA synchrotron. HR STEM measurements were performed at DME-UCA in Cadiz University with financial support from FEDER/MINECO (MAT2017-87579-R and MAT2016-81118-P). A relevant patent application (European patent application No. 19382024.8) has been presented. C.W.L. thanks CAPES (Science without Frontiers-Process no. 13191/13-6) for a predoctoral fellowship.

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Authors and Affiliations

  1. Instituto de Tecnología Química, Universitat Politècnica de València–Consejo Superior de Investigaciones Científicas, Valencia, Spain

    Lichen Liu, Christian W. Lopes, Chengeng Li, Patricia Concepcion & Avelino Corma

  2. Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Universidad de Cádiz, Cádiz, Spain

    Miguel Lopez-Haro & Jose J. Calvino

  3. ALBA Synchrotron Light Source, Barcelona, Spain

    Laura Simonelli

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Contributions

A.C. conceived the project, directed the study and wrote the manuscript. L.L. carried out the synthesis, characterizations and catalytic measurements and collaborated in writing the manuscript. M.L.-H. and J.J.C. carried out the HR STEM measurements, image analysis and simulations. C.W.L. carried out the analysis of XAS data. L.L., C.L. and L.S. contributed to the collection of XAS data in the ALBA synchrotron. P.C. carried out the CO infrared adsorption experiments. All the authors discussed the results and contributed to the production of the manuscript.

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Correspondence to Avelino Corma.

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Supplementary Tables 1–5, Supplementary Figs. 1–71 and Supplementary refs. 1–8.

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Liu, L., Lopez-Haro, M., Lopes, C.W. et al. Regioselective generation and reactivity control of subnanometric platinum clusters in zeolites for high-temperature catalysis. Nat. Mater. 18, 866–873 (2019). https://doi.org/10.1038/s41563-019-0412-6

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