Article | Published:

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

Nature Catalysisvolume 1pages540546 (2018) | Download Citation

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

References

  1. 1.

    Ertl, G., Knözinger, H., Schüth, F. & Weitkamp, J. Handbook of Heterogeneous Catalysis (Wiley, Weinheim, 2008).

  2. 2.

    Behrens, M. et al. The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science 336, 893–897 (2012).

  3. 3.

    Lu, J. et al. Coking- and sintering-resistant palladium catalysts achieved through atomic layer deposition. Science 335, 1205–1208 (2012).

  4. 4.

    Li, W.-Z. et al. Stable platinum nanoparticles on specific MgAl2O4 spinel facets at high temperatures in oxidizing atmospheres. Nat. Chem. 4, 2481 (2013).

  5. 5.

    Prieto, G., Zečević, J., Friedrich, H., de Jong, K. P. & de Jongh, P. E. Towards stable catalysts by controlling collective properties of supported metal nanoparticles. Nat. Mater. 12, 34–39 (2013).

  6. 6.

    Tang, H. et al. Strong metal–support interactions between gold nanoparticles and nonoxides. J. Am. Chem. Soc. 138, 56–59 (2016).

  7. 7.

    Ta, N. et al. Stabilized gold nanoparticles on ceria nanorods by strong interfacial anchoring. J. Am. Chem. Soc. 134, 20585–20588 (2012).

  8. 8.

    Zhao, M.-Q. et al. Embedded high density metal nanoparticles with extraordinary thermal stability derived from guest-host mediated layered double hydroxides. J. Am. Chem. Soc. 132, 14739–14741 (2010).

  9. 9.

    Tang, H. et al. Ultrastable hydroxyapatite/titanium-dioxide-supported gold nanocatalyst with strong metal–support interaction for carbon monoxide oxidation. Angew. Chem. Int. Ed. 55, 10606–10611 (2016).

  10. 10.

    Sattler, J. J. H. B. et al. Platinum-promoted Ga/Al2O3 as highly active, selective, and stable catalyst for the dehydrogenation of propane. Angew. Chem. Int. Ed. 53, 9251–9256 (2014).

  11. 11.

    Zhang, L. Y. et al. Stabilization of palladium nanoparticles on nanodiamond–graphene core–shell supports for CO oxidation. Angew. Chem. Int. Ed. 54, 15823–15826 (2015).

  12. 12.

    Shi, L. et al. Al2O3 nanosheets rich in pentacoordinate Al3+ ions stabilize Pt–Sn clusters for propane dehydrogenation. Angew. Chem. Int. Ed. 54, 13994–13998 (2015).

  13. 13.

    Wang, S. et al. Aggregation-free gold nanoparticles in ordered mesoporous carbons: toward highly active and stable heterogeneous catalysts. J. Am. Chem. Soc. 135, 11849–11860 (2013).

  14. 14.

    Zhou, H. P. et al. Thermally stable Pt/CeO2 hetero-nanocomposites with high catalytic activity. J. Am. Chem. Soc. 132, 4998–4999 (2010).

  15. 15.

    Farrauto, R. J. & Bartholomew, C. H. Fundamentals of Industrial Catalytic Process (Blackie, London, 1997).

  16. 16.

    Morgan, K., Goguet, A. & Hardacre, C. Metal redispersion strategies for recycling of supported metal catalysts: a perspective. ACS Catal. 5, 3430–3445 (2015).

  17. 17.

    Dick, K., Dhanasekaran, T., Zhang, Z. Y. & Meisel, D. Size-dependent melting of silica-encapsulated gold nanoparticles. J. Am. Chem. Soc. 124, 2312–2317 (2002).

  18. 18.

    Joo, S. H. et al. Thermally stable Pt/mesoporous silica core–shell nanocatalysts for high-temperature reactions. Nat. Mater. 8, 126–131 (2009).

  19. 19.

    Yu, K., Wu, Z. C., Zhao, Q. R., Li, B. X. & Xie, Y. High-temperature-stable Au@SnO2 core/shell supported catalyst for CO oxidation. J. Phys. Chem. C 112, 2244–2247 (2008).

  20. 20.

    Cargnello, M. et al. Exceptional activity for methane combustion over modular Pd@CeO2 subunits on functionalized Al2O3. Science 337, 713–717 (2012).

  21. 21.

    Arnal, P. M., Comotti, M. & Schüth, F. High-temperature-stable catalysts by hollow sphere encapsulation. Angew. Chem. Int. Ed. 45, 8224–8227 (2006).

  22. 22.

    O’Neill, B. J. et al. Stabilization of copper catalysts for liquid-phase reactions by atomic layer deposition. Angew. Chem. Int. Ed. 52, 13808–13812 (2013).

  23. 23.

    Zhan, W. et al. A sacrificial coating strategy toward enhancement of metal–support interaction for ultrastable Au nanocatalysts. J. Am. Chem. Soc. 138, 16130–16139 (2016).

  24. 24.

    Huang, W. et al. Low-temperature transformation of methane to methanol on Pd1O4 single sites anchored on the internal surface of microporous silicate. Angew. Chem., Int. Ed. 55, 13441–13445 (2016).

  25. 25.

    Laursen, A. B. et al. Substrate size-selective catalysis with zeolite-encapsulated gold nanoparticles. Angew. Chem. Int. Ed. 49, 3504–3507 (2010).

  26. 26.

    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).

  27. 27.

    Wang, N. et al. In situ confinement of ultrasmall Pd clusters within nanosized silicalite-1 zeolite for highly efficient catalysis of hydrogen generation. J. Am. Chem. Soc. 138, 7484–7487 (2016).

  28. 28.

    Liu, L. et al. Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D. Nat. Mater. 16, 132–138 (2017).

  29. 29.

    Bond, G. C., Louis, C. & Thompson, D. T. Catalysis by Gold (Imperial College Press, London, 2006).

  30. 30.

    Iglesias-Juez, A., Kubacka, A., Fernández-García, M., Michiel, M. D. & Newton, M. A. Nanoparticulate Pd supported catalysts: size-dependent formation of Pd(I)/Pd(0) and their role in CO elimination. J. Am. Chem. Soc. 133, 4484–4489 (2011).

  31. 31.

    Xiao, F. S., Weber, W. A., Alexeev, O. & Gates, B. C. Probing the limits of structure insensitivity: size-dependent catalytic activity of Al2O3-supported iridium clusters and particles for toluene hydrogenation. Stud. Surf. Sci. Catal. 101, 1135–1144 (1996).

  32. 32.

    Kistler, J. D. et al. A single-site platinum CO oxidation catalyst in zeolite KLTL: microscopic and spectroscopic determination of the locations of the platinum atoms. Angew. Chem. Int. Ed. 53, 8904–8907 (2014).

  33. 33.

    Cui, T.-L. et al. Encapsulating palladium nanoparticles inside mesoporous MFI zeolite nanocrystals for shape-selective catalysis. Angew. Chem. Int. Ed. 55, 9178–9182 (2016).

  34. 34.

    Wang, C. et al. Product selectivity controlled by zeolite crystals in biomass hydrogenation over a palladium catalyst. J. Am. Chem. Soc. 138, 7880–7883 (2016).

  35. 35.

    Sachtler, W. M. H. Metal clusters in zeolites: an intriguing class of catalysts. Acc. Chem. Res. 26, 383–387 (1993).

  36. 36.

    Sun, T. & Seff, K. Silver clusters and chemistry in zeolites. Chem. Rev. 94, 857–870 (1994).

  37. 37.

    Guzman, J. in Model Systems in Catalysis (ed. Rioux, R.) Ch. 19 (Springer, New York, 2010).

  38. 38.

    Creyghton, E. J. & Downing, R. S. Shape-selective hydrogenation and hydrogen transfer reactions over zeolite catalysts. J. Mol. Catal. A 134, 47–61 (1998).

  39. 39.

    Alexeev, O. S. & Gates, B. C. Supported bimetallic cluster catalysts. Ind. Eng. Chem. Res. 42, 1571–1587 (2003).

  40. 40.

    Yamamoto, T., Shido, T., Inagaki, S., Fukushima, Y. & Ichikawa, M. Ship-in-bottle synthesis of [Pt15(CO)30]2– encapsulated in ordered hexagonal mesoporous channels of FSM-16 and their effective catalysis in water-gas shift reaction. J. Am. Chem. Soc. 118, 5810–5811 (1996).

  41. 41.

    Rodriguez, J. A. et al. Activity of CeOx and TiOx nanoparticles grown on Au(111) in the water-gas shift reaction. Science 318, 1757–1760 (2007).

  42. 42.

    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).

  43. 43.

    Yang, M. et al. A common single-site Pt(II)–O(OH)x– species stabilized by sodium on “active” and “inert” supports catalyzes the water-gas shift reaction. J. Am. Chem. Soc. 137, 3470–3473 (2015).

  44. 44.

    Chen, M. S., Cai, Y., Yan, Z. & Goodman, D. W. On the origin of the unique properties of supported Au nanoparticles. J. Am. Chem. Soc. 128, 6341–6346 (2006).

  45. 45.

    Ouyang, R. & Li, W.-X. Adsorbed CO induced change of the adsorption site and charge of Au adatoms on FeO(111)/Ru(0001). Chin. J. Catal. 34, 1820–1825 (2013).

  46. 46.

    Fu, Q. et al. Interface-confined ferrous centers for catalytic oxidation. Science 328, 1141–1144 (2010).

  47. 47.

    Chen, G. et al. Interfacial effects in iron–nickel hydroxide–platinum nanoparticles enhance catalytic oxidation. Science 344, 495–499 (2014).

  48. 48.

    Hickman, D. A. & Schmidt, L. D. Production of syngas by direct catalytic oxidation of methane. Science 259, 343–346 (1993).

  49. 49.

    Ayabe, S. et al. Catalytic autothermal reforming of methane and propane over supported metal catalysts. Appl. Catal. A 241, 261–269 (2003).

  50. 50.

    Carrasquillo-Flores, R. et al. Reverse water-gas shift on interfacial sites formed by deposition of oxidized molybdenum moieties onto gold nanoparticles. J. Am. Chem. Soc. 137, 10317–10325 (2015).

Download references

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).

Author information

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

Authors

  1. Search for Jian Zhang in:

  2. Search for Liang Wang in:

  3. Search for Bingsen Zhang in:

  4. Search for Haishuang Zhao in:

  5. Search for Ute Kolb in:

  6. Search for Yihan Zhu in:

  7. Search for Lingmei Liu in:

  8. Search for Yu Han in:

  9. Search for Guoxiong Wang in:

  10. Search for Chengtao Wang in:

  11. Search for Dang Sheng Su in:

  12. Search for Bruce C. Gates in:

  13. Search for Feng-Shou Xiao in:

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.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Liang Wang or Feng-Shou Xiao.

Supplementary information

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41929-018-0098-1