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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

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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.

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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.

References

  1. Boronat, M., Leyva-Perez, A. & Corma, A. Theoretical and experimental insights into the origin of the catalytic activity of subnanometric gold clusters: attempts to predict reactivity with clusters and nanoparticles of gold. Acc. Chem. Res. 47, 834–844 (2014).

    Article  CAS  Google Scholar 

  2. Flytzani-Stephanopoulos, M. & Gates, B. C. Atomically dispersed supported metal catalysts. Ann. Rev. Chem. Bio. Eng. 3, 545–574 (2012).

    Article  CAS  Google Scholar 

  3. Gates, B. C. Supported metal clusters: synthesis, structure, and catalysis. Chem. Rev. 95, 511–522 (1995).

    Article  CAS  Google Scholar 

  4. Corma, A. et al. Exceptional oxidation activity with size-controlled supported gold clusters of low atomicity. Nat. Chem. 5, 775–781 (2013).

    Article  CAS  Google Scholar 

  5. Yang, M. et al. Catalytically active Au-O(OH)x-species stabilized by alkali ions on zeolites and mesoporous oxides. Science 346, 1498–1501 (2014).

    Article  CAS  Google Scholar 

  6. Rivallan, M. et al. Platinum sintering on H-ZSM-5 followed by chemometrics of CO adsorption and 2D pressure-jump IR spectroscopy of adsorbed species. Angew. Chem. Int. Ed. 49, 785–789 (2010).

    Article  CAS  Google Scholar 

  7. Zecevic, J., van der Eerden, A. M., Friedrich, H., de Jongh, P. E. & de Jong, K. P. Heterogeneities of the nanostructure of platinum/zeolite Y catalysts revealed by electron tomography. ACS Nano 7, 3698–3705 (2013).

    Article  CAS  Google Scholar 

  8. Philippaerts, A. et al. Unprecedented shape selectivity in hydrogenation of triacylglycerol molecules with Pt/ZSM-5 zeolite. Angew. Chem. Int. Ed. 50, 3947–3949 (2011).

    Article  CAS  Google Scholar 

  9. Kim, J., Kim, W., Seo, Y., Kim, J.-C. & Ryoo, R. n-Heptane hydroisomerization over Pt/MFI zeolite nanosheets: effects of zeolite crystal thickness and platinum location. J. Catalys. 301, 187–197 (2013).

    Article  CAS  Google Scholar 

  10. Goel, S., Wu, Z., Zones, S. I. & Iglesia, E. Synthesis and catalytic properties of metal clusters encapsulated within small-pore (SOD, GIS, ANA) zeolites. J. Am. Chem. Soc. 134, 17688–17695 (2012).

    Article  CAS  Google Scholar 

  11. Choi, M., Wu, Z. & Iglesia, E. Mercaptosilane-assisted synthesis of metal clusters within zeolites and catalytic consequences of encapsulation. J. Am. Chem. Soc. 132, 9129–9137 (2010).

    Article  CAS  Google Scholar 

  12. Choi, M., Yook, S. & Kim, H. Hydrogen spillover in encapsulated metal catalysts: new opportunities for designing advanced hydroprocessing catalysts. ChemCatChem 7, 1048–1057 (2015).

    Article  CAS  Google Scholar 

  13. Kulkarni, A., Lobo-Lapidus, R. J. & Gates, B. C. Metal clusters on supports: synthesis, structure, reactivity, and catalytic properties. Chem. Commun. 46, 5997–6015 (2010).

    Article  CAS  Google Scholar 

  14. Guzman, J. & Gates, B. C. Supported molecular catalysts: metal complexes and clusters on oxides and zeolites. Dalton Trans. 1, 3303–3318 (2003).

    Article  Google Scholar 

  15. Leonowicz, M. E., Lawton, J. A., Lawton, S. L. & Rubin, M. K. MCM-22: a molecular sieve with two independent multidimensional channel systems. Science 264, 1910–1913 (1994).

    Article  CAS  Google Scholar 

  16. Camblor, M. A. et al. A new microporous polymorph of silica isomorphous to zeolite MCM-22. Chem. Mater. 8, 2415–2417 (1996).

    Article  CAS  Google Scholar 

  17. Hyotanishi, M., Isomura, Y., Yamamoto, H., Kawasaki, H. & Obora, Y. Surfactant-free synthesis of palladium nanoclusters for their use in catalytic cross-coupling reactions. Chem. Commun. 47, 5750–5752 (2011).

    Article  CAS  Google Scholar 

  18. Duchesne, P. N. & Zhang, P. Local structure of fluorescent platinum nanoclusters. Nanoscale 4, 4199–4205 (2012).

    Article  CAS  Google Scholar 

  19. Lu, J., Aydin, C., Browning, N. D. & Gates, B. C. Imaging isolated gold atom catalytic sites in zeolite NaY. Angew. Chem. Int. Ed. 51, 5842–5846 (2012).

    Article  CAS  Google Scholar 

  20. Yacamán, M. J., Santiago, U. & Mejía-Rosales, S. in Advanced Transmission Electron Microscopy: Applications to Nanomaterials (eds Francis, L., Mayoral, A. & Arenal, R.) 1–29 (Springer, 2015).

    Book  Google Scholar 

  21. Jena, P., Khanna, S. N. & Rao, B. K. Physics and Chemistry of Finite Systems: From Clusters to Crystals (Springer, 1992).

    Book  Google Scholar 

  22. Yamasaki, J. et al. Ultramicroscopy 151, 224–231 (2015).

    Article  CAS  Google Scholar 

  23. Sohlberg, K., Pennycook, T. J., Zhoud, W. & Pennycook, S. J. Insights into the physical chemistry of materials from advances in HAADF-STEM. Phys. Chem. Chem. Phys. 17, 3982–4006 (2015).

    Article  CAS  Google Scholar 

  24. Aydin, C., Lu, J., Browning, N. D. & Gates, B. C. A ‘smart’ catalyst: sinter-resistant supported iridium clusters visualized with electron microscopy. Angew. Chem. Int. Ed. 51, 5929–5934 (2012).

    Article  CAS  Google Scholar 

  25. Wei, H. et al. FeOx-supported platinum single-atom and pseudo-single-atom catalysts for chemoselective hydrogenation of functionalized nitroarenes. Nat. Commun. 5, 5634 (2014).

    Article  CAS  Google Scholar 

  26. Addou, R. et al. Influence of hydroxyls on Pd atom mobility and clustering on rutile TiO2(011)-2 × 1. ACS Nano 8, 6321–6333 (2014).

    Article  CAS  Google Scholar 

  27. Jung, U. et al. Comparative in operando studies in heterogeneous catalysis: atomic and electronic structural features in the hydrogenation of ethylene over supported Pd and Pt catalysts. ACS Catal. 5, 1539–1551 (2015).

    Article  CAS  Google Scholar 

  28. Agostini, G. et al. Effect of different face centered cubic nanoparticle distributions on particle size and surface area determination: a theoretical study. J. Phys. Chem. C 118, 4085–4094 (2014).

    Article  CAS  Google Scholar 

  29. Alexeev, O. & Gates, B. C. EXAFS characterization of supported metal-complex and metal-cluster catalysts made from organometallic precursors. Top. Catal. 10, 273–293 (2000).

    Article  CAS  Google Scholar 

  30. Chakraborty, I., Bhuin, R. G., Bhat, S. & Pradeep, T. Blue emitting undecaplatinum clusters. Nanoscale 6, 8561–8564 (2014).

    Article  CAS  Google Scholar 

  31. Zheng, J., Nicovich, P. R. & Dickson, R. M. Highly fluorescent noble-metal quantum dots. Ann. Rev. Phys. Chem. 58, 409–431 (2007).

    Article  CAS  Google Scholar 

  32. Okrut, A. et al. Selective molecular recognition by nanoscale environments in a supported iridium cluster catalyst. Nat. Nanotech. 9, 459–465 (2014).

    Article  CAS  Google Scholar 

  33. Zhou, C. et al. On the sequential hydrogen dissociative chemisorption on small platinum clusters: a density functional theory study. J. Phys. Chem. C 111, 12773–12778 (2007).

    Article  CAS  Google Scholar 

  34. De La Cruz, C. & Sheppard, N. An exploration of the surfaces of some Pt/SiO2 catalysts using CO as an infrared spectroscopic probe. Spectrochim. Acta A 50, 271–285 (1994).

    Article  Google Scholar 

  35. Klünker, C., Balden, M., Lehwald, S. & Daum, W. CO stretching vibrations on Pt(111) and Pt(110) studied by sum frequency generation. Surf. Sci. 360, 104–111 (1996).

    Article  Google Scholar 

  36. Stakheev, A. Y., Shpiro, E. S., Jaeger, N. I. & Schulz-Ekloff, G. Electronic state and location of Pt metal clusters in KL zeolite: FTIR study of CO chemisorption. Catal. Lett. 32, 147–158 (1995).

    Article  CAS  Google Scholar 

  37. Heiz, U., Sanchez, A., Abbet, S. & Schneider, W. D. Catalytic oxidation of carbon monoxide on monodispersed platinum clusters: each atom counts. J. Am. Chem. Soc. 121, 3214–3217 (1999).

    Article  CAS  Google Scholar 

  38. Levitas, V. I. & Samani, K. Size and mechanics effects in surface-induced melting of nanoparticles. Nat. Commun. 2, 284 (2011).

    Article  Google Scholar 

  39. Jiang, H., Moon, K.-s., Dong, H., Hua, F. & Wong, C. P. Size-dependent melting properties of tin nanoparticles. Chem. Phys. Lett. 429, 492–496 (2006).

    Article  CAS  Google Scholar 

  40. Nanda, K. K., Kruis, F. E. & Fissan, H. Evaporation of free PbS nanoparticles: evidence of the Kelvin effect. Phys. Rev. Lett. 89, 256103 (2002).

    Article  CAS  Google Scholar 

  41. Vajda, S. et al. Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane. Nat. Mater. 8, 213–216 (2009).

    Article  CAS  Google Scholar 

  42. Ortalan, V., Uzun, A., Gates, B. C. & Browning, N. D. Direct imaging of single metal atoms and clusters in the pores of dealuminated HY zeolite. Nat. Nanotech. 5, 506–510 (2010).

    Article  CAS  Google Scholar 

  43. Koch, C. Determination of Core Structure Periodicity and Point Defect Density along Dislocations PhD thesis, Univ. Arizona (2002).

  44. Mathon, O. et al. The time-resolved and extreme conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the general-purpose EXAFS bending-magnet beamline BM23. J. Synchrotron Radiat. 22, 1548–1554 (2015).

    Article  CAS  Google Scholar 

  45. Newville, M. IFEFFIT: interactive XAFS analysis and FEFF fitting. J. Synchrotron Radiat. 8, 322–324 (2001).

    Article  CAS  Google Scholar 

Download references

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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