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Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D

Nature Materials volume 16, pages 132–138 (2017)Cite this article

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A Corrigendum to this article was published on 01 December 2017

An Erratum to this article was published on 25 April 2017

This article has been updated

Abstract

Single metal atoms and metal clusters have attracted much attention thanks to their advantageous capabilities as heterogeneous catalysts. However, the generation of stable single atoms and clusters on a solid support is still challenging. Herein, we report a new strategy for the generation of single Pt atoms and Pt clusters with exceptionally high thermal stability, formed within purely siliceous MCM-22 during the growth of a two-dimensional zeolite into three dimensions. These subnanometric Pt species are stabilized by MCM-22, even after treatment in air up to 540 °C. Furthermore, these stable Pt species confined within internal framework cavities show size-selective catalysis for the hydrogenation of alkenes. High-temperature oxidation–reduction treatments result in the growth of encapsulated Pt species to small nanoparticles in the approximate size range of 1 to 2 nm. The stability and catalytic activity of encapsulated Pt species is also reflected in the dehydrogenation of propane to propylene.

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Figure 1: Illustration of the preparation of Pt@MCM-22.
Figure 2: Atomic structures of Pt@MCM-22.
Figure 3: Characterization of Pt@MCM-22 and Pt/MCM-22-imp.
Figure 4: Reaction rates of Pt@MCM-22 and Pt/MCM-22-imp in hydrogenation of light olefins.
Figure 5: Pt@MCM-22 after high-temperature oxidation–reduction treatments.

Change history

  • 25 October 2017

    In the version of this Article originally published, the four instances of the window type on page 136 should have read '10-MR'. On the same page, in the 'Catalytic activity' section, the accessibility of isobutene was incorrectly described, and the phrase should have read 'isobutene is mainly accessible to Pt species located at the external cups on the surface of MCM-22'. These changes do not affect the results of the Article.

  • 24 March 2017

    In the version of this Article originally published, Fig. 5e showed the wrong graph. This has now been corrected in all versions.

  • 25 April 2017

    Nature Materials 16, 132–138 (2016); published online 20 December 2016; corrected after print 24 March 2017 In the version of this Article originally published, Fig. 5e showed the wrong graph. This has now been corrected in all versions. The correct figure is shown below.

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Acknowledgements

This work was funded by the Spanish Government (Consolider Ingenio 2010-MULTICAT (CSD2009-00050) and MAT2014-52085-C2-1-P) and by the Generalitat Valenciana (Prometeo). The Severo Ochoa Program (SEV-2012-0267) is gratefully acknowledged. L.L. thanks ITQ for a contract. The authors also thank the Microscopy Service of UPV for the TEM and STEM measurements. The HAADF-HRSTEM works were conducted in the Laboratorio de Microscopias Avanzadas (LMA) at the Instituto de Nanociencia de Aragon (INA)-Universidad de Zaragoza (Spain), a Spanish ICTS National Facility. Some of the research leading to these results has received funding from the European Union Seventh Framework Program under Grant Agreement 312483-ESTEEM2 (Integrated Infrastructure Initiative-I3). R.A. also acknowledges funding from the Spanish Ministerio de Economia y Competitividad (FIS2013-46159-C3-3-P) and the European Union Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No. 642742.

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Authors and Affiliations

  1. Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas (UPV-CSIC), Av. de los Naranjos s/n, 46022 Valencia, Spain

    Lichen Liu, Urbano Díaz, Patricia Concepción & Avelino Corma

  2. Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, Universidad de Zaragoza, Mariano Esquillor Edificio I+D, 50018 Zaragoza, Spain

    Raul Arenal

  3. ARAID Foundation, 50018 Zaragoza, Spain

    Raul Arenal

  4. European Synchrotron Radiation Facility, 6 rue Jules Horowitz, Grenoble, BP 156, F-38042, France

    Giovanni Agostini

  5. King Fahd University of Petroleum and Minerals, PO Box 989, Dhahran 31261, Saudi Arabia

    Avelino Corma

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Contributions

A.C. conceived the project, directed the study and wrote the manuscript. L.L. carried out the synthesis, characterization and catalytic measurements and collaborated in writing the manuscript. U.D. participated in the synthesis and characterization of the materials. R.A. performed the high-resolution STEM characterization. G.A. performed the XAS measurement and analysed the data. P.C. carried out the H2–D2 exchange and CO-IR adsorption experiments. U.D., R.A., G.A. and P.C. also collaborated in writing the manuscript.

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Correspondence to Avelino Corma.

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Liu, L., Díaz, U., Arenal, R. et al. Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nature Mater 16, 132–138 (2017). https://doi.org/10.1038/nmat4757

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