Skip to main content
SpringerLink
Log in

Nanoparticles@nanoscale metal-organic framework composites as highly efficient heterogeneous catalysts for size- and shape-selective reactions

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Composites incorporating nanoparticles (NPs) within metal-organic frameworks (MOFs) find applications in many different fields. In particular, using MOF layers as molecular sieves built on the NPs could enable selectivity in heterogeneous catalysis. However, such composites typically exhibit low catalytic efficiency, due to the slow diffusion of the reactants in the long and narrow channels of the MOF shell. In order to improve the catalytic efficiency of these systems, here we report the fabrication of NPs incorporated in nanosized MOFs (NPs@nano-MOFs), obtained by reducing the size of the MOF crystals grown around the NPs. The crystal size of the composites was controlled by modulating the nucleation rate of the MOFs during the encapsulation of pre-synthesized and catalytically active NPs; in this way, NPs@MOF crystals smaller than 50 nm were synthesized and subsequently used as highly efficient catalysts. Due to the shorter path from the MOF surface to the active sites, the obtained Pt@nano-MOFs composites showed a higher conversion rate than their larger-sized counterparts in the synthesis of imines via cascade reaction of nitrobenzene and in the hydrogenation of olefins, while retaining the excellent size and shape selectivity associated with the molecular sieving effect of the MOF layer. The present strategy can also be applied to prepare other encapsulated nanostructures combining various types of NPs and nano-MOFs, thus highlighting the broad potential of this approach for developing optimized catalysts with high reactivity and selectivity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Dhakshinamoorthy, A.; Garcia, H. Catalysis by metal nanoparticles embedded on metal-organic frameworks. Chem. Soc. Rev. 2012, 41, 5262–5284.

    Article  Google Scholar 

  2. Moon, H. R.; Lim, D. W.; Suh, M. P. Fabrication ofmetal nanoparticles in metal-organic frameworks. Chem. Soc. Rev. 2013, 42, 1807–1824.

    Article  Google Scholar 

  3. Hu, P.; Morabito, J. V.; Tsung, C. K. Core–shell catalysts of metal nanoparticle core and metal-organic framework shell. ACS Catal. 2014, 4, 4409–4419.

    Article  Google Scholar 

  4. Liu, Y. L.; Tang, Z. Y. Multifunctional nanoparticle@MOF core-shell nanostructures. Adv. Mater. 2013, 25, 5819–5825.

    Article  Google Scholar 

  5. Xu, X. B.; Zhang, Z. C.; Wang, X. Well-defined metal-organic-framework hollow nanostructures for catalytic reactions involving gases. Adv. Mater. 2015, 27, 5365–5371.

    Article  Google Scholar 

  6. Aijaz, A.; Karkamkar, A.; Choi, Y. J.; Tsumori, N.; Rönnebro, E.; Autrey, T.; Shioyama, H.; Xu, Q. Immobilizing highly catalytically active Pt nanoparticles inside the pores of metal-organic framework: A double solvents approach. J. Am. Chem. Soc. 2012, 134, 13926–13929.

    Article  Google Scholar 

  7. Hou, C.; Zhao, G. F.; Ji, Y. J.; Niu, Z. Q.; Wang, D. S.; Li, Y. D.Hydroformylation of alkenes over rhodium supported on the metal-organic framework ZIF-8. Nano Res. 2014, 7, 1364–1369.

    Article  Google Scholar 

  8. Liu, H. L.; Chang, L.; Bai, C. H.; Chen, L. Y.; Luque, R.; Li, Y. W. Controllable encapsulation of “clean” metal clusters within MOFs through kinetic modulation: Towards advanced heterogeneous nanocatalysts. Angew. Chem., Int. Ed. 2016, 55, 5019–5023.

    Article  Google Scholar 

  9. Choi, K. M.; Na, K.; Somorjai, G. A.; Yaghi, O. M. Chemical environment control and enhanced catalytic performance of platinum nanoparticles embedded in nanocrystalline metalorganic frameworks. J. Am. Chem. Soc. 2015, 137, 7810–7816.

    Article  Google Scholar 

  10. Zhao, M. T.; Yuan, K.; Wang, Y.; Li, G. D.; Guo, J.; Gu, L.; Hu, W. P.; Zhao, H. J.; Tang, Z. Y. Metal-organic frameworks as selectivity regulators for hydrogenation reactions. Nature 2016, 539, 76–80.

    Article  Google Scholar 

  11. Yang, Q.; Liu, W. X.; Wang, B. Q.; Zhang, W. N.; Zeng, X. Q.; Zhang, C.; Qin, Y. J.; Sun, X. M.; Wu, T. P.; Liu, J. F. et al. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency. Nat. Commun. 2017, 8, 14429.

    Article  Google Scholar 

  12. Yang, J.; Zhang, F. J.; Lu, H. Y.; Hong, X.; Jiang, H. L.; Wu, Y. E.; Li, Y. D. Hollow Zn/Co ZIF particles derived from core–shell ZIF-67@ZIF-8 as selective catalyst for the semi-hydrogenation of acetylene. Angew. Chem., Int. Ed. 2015, 54, 10889–10893.

    Article  Google Scholar 

  13. Xu, Z. L.; Zhang, W. N.; Weng, J. N.; Huang, W.; Tian, D. B.; Huo, F. W. Encapsulation of metal layers within metal-organic frameworks as hybrid thin films for selective catalysis. Nano Res. 2016, 9, 158–164.

    Article  Google Scholar 

  14. Li, Z.; Yu, R.; Huang, J. L.; Shi, Y. S.; Zhang, D. Y.; Zhong, X. Y.; Wang, D. S.; Wu, Y.; Li, Y. D. Platinum-nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving. Nat. Commun. 2015, 6, 8248.

    Article  Google Scholar 

  15. Lu, G.; Li, S. Z.; Guo, Z.; Farha, O. K.; Hauser, B. G.; Qi, X. Y.; Wang, Y.; Wang, X.; Han, S. Y.; Liu, X. G. et al. Imparting functionality to a metal-organic framework material by controlled nanoparticle encapsulation. Nat. Chem. 2012, 4, 310–316.

    Article  Google Scholar 

  16. Liu, Y. Y.; Zhang, W. N.; Li, S. Z.; Cui, C. L.; Wu, J.; Chen, H. Y.; Huo, F. W. Designable yolk–shell nanoparticle@ MOFpetalousheterostructures. Chem. Mater. 2014, 26, 1119–1125.

    Article  Google Scholar 

  17. Yang, Q. H.; Xu, Q.; Yu, S. H.; Jiang, H. L. Pd nanocubes@ ZIF-8: Integration of plasmon-driven photothermal conversion with a metal-organic framework for efficient and selective catalysis. Angew. Chem. 2016, 128, 3749–3753.

    Article  Google Scholar 

  18. Kuo, C. H.; Tang, Y.; Chou, L. Y.; Sneed, B. T.; Brodsky, C. N.; Zhao, Z. P.; Tsung, C. K. Yolk–shell nanocrystal@ZIF-8 nanostructures for gas-phase heterogeneous catalysis with selectivity control. J. Am. Chem. Soc. 2012, 134, 14345–14348.

    Article  Google Scholar 

  19. Zeng, M.; Chai, Z. G.; Deng, X.; Li, Q.; Feng, S. Q.; Wang, J.; Xu, D. S. Core–shell CdS@ZIF-8 structures for improved selectivity in photocatalytic H2 generation from formic acid. Nano Res. 2016, 9, 2729–2734.

    Article  Google Scholar 

  20. Zhao, M. T.; Deng, K.; He, L. C.; Liu, Y.; Li, G. D.; Zhao, H. J.; Tang, Z. Y. Core–shell palladium nanoparticle@metalorganic frameworks as multifunctional catalysts for cascade reactions. J. Am. Chem. Soc. 2014, 136, 1738–1741.

    Article  Google Scholar 

  21. Na, K.; Choi, K. M.; Yaghi, O. M.; Somorjai, G. A. Metal nanocrystals embedded in single nanocrystals of MOFs give unusual selectivity as heterogeneous catalysts. Nano Lett. 2014, 14, 5979–5983.

    Article  Google Scholar 

  22. Zhang, W. N.; Lu, G.; Cui, C. L.; Liu, Y. Y.; Li, S. Z.; Yan, W. J.; Xing, C.; Chi, Y. R.; Yang, Y. H.; Huo, F. W.A family of metal-organic frameworks exhibiting size-selective catalysis with encapsulated noble-metal nanoparticles. Adv. Mater. 2014, 26, 4056–4060.

    Article  Google Scholar 

  23. Zhang, W. N.; Liu, Y. Y.; Lu, G.; Wang, Y.; Li, S. Z.; Cui, C. L.; Wu, J.; Xu, Z. L.; Tian, D. B.; Huang, W. et al. Mesoporous metal-organic frameworks with size-, shape-, and space-distribution-controlled pore structure. Adv. Mater. 2015, 27, 2923–2929.

    Article  Google Scholar 

  24. Huang, Y. B.; Shen, M.; Wang, X. S.; Shi, P. C.; Li, H. F.; Cao, R. Hierarchically micro-and mesoporous metal-organic framework-supported alloy nanocrystals as bifunctional catalysts: Toward cooperative catalysis. J. Catal. 2015, 330, 452–457.

    Article  Google Scholar 

  25. Zhang, Z. C.; Chen, Y. F.; He, S.; Zhang, J. C.; Xu, X. B.; Yang, Y.; Nosheen, F.; Saleem, F.; He, W.; Wang, X. Hierarchical Zn/Ni-MOF-2 nanosheet-assembled hollow nanocubes for multicomponent catalytic reactions. Angew. Chem., Int. Ed. 2014, 53, 12517–12521.

    Google Scholar 

  26. Liu, W.; Huang, J.; Yang, Q.; Wang, S.; Sun, X.; Zhang, W.; Liu, J.; Huo, F. Multi-shelled hollow metal-organic frameworks. Angew. Chem., Int. Ed. 2017, 129, 5604–5608.

    Article  Google Scholar 

  27. Xu, X. B.; Lu, Y.; Yang, Y.; Nosheen, F.; Wang, X. Tuning the growth of metal-organic framework nanocrystals by using polyoxometalates as coordination modulators. Sci. China Mater. 2015, 58, 370–377.

    Article  Google Scholar 

  28. Zhang, Z. C.; Chen, Y. F.; Xu, X. B.; Zhang, J. C.; Xiang, G. L.; He, W.; Wang, X. Well-defined metal-organic framework hollow nanocages. Angew. Chem., Int. Ed. 2014, 53, 429–433.

    Article  Google Scholar 

  29. Ni, Z.; Masel, R. I. Rapid production of metal-organic frameworks via microwave-assisted solvothermal synthesis. J. Am. Chem. Soc. 2006, 128, 12394–12395.

    Article  Google Scholar 

  30. Rieter, W. J.; Taylor, K. M. L.; Lin, W. B. Surface modification and functionalization of nanoscale metal-organic frameworks for controlled release and luminescence sensing. J. Am. Chem. Soc. 2007, 129, 9852–9853.

    Article  Google Scholar 

  31. Tsuruoka, T.; Furukawa, S.; Takashima, Y.; Yoshida, K.; Isoda, S.; Kitagawa, S. Nanoporousnanorods fabricated by coordination modulation and oriented attachment growth. Angew. Chem., Int. Ed. 2009, 48, 4739–4743.

    Article  Google Scholar 

  32. Schaate, A.; Roy, P.; Godt, A.; Lippke, J.; Waltz, F.; Wiebcke, M.; Behrens, P. Modulated synthesis of Zr-based metal-organic frameworks: From nano to single crystals. Chem.—Eur. J. 2011, 17, 6643–6651.

    Article  Google Scholar 

  33. Diring, S.; Furukawa, S.; Takashima, Y.; Tsuruoka, T.; Kitagawa, S. Controlled multiscale synthesis of porous coordination polymer in nano/micro regimes. Chem. Mater. 2010, 22, 4531–4538.

    Article  Google Scholar 

  34. Lu, G.; Cui, C. L.; Zhang, W. N.; Liu, Y. Y.; Huo, F. W. Synthesis and self-assembly of monodispersed metal-organic framework microcrystals. Chem.—Asian J. 2013, 8, 69–72.

    Article  Google Scholar 

  35. Cravillon, J.; Münzer, S.; Lohmeier, S. J.; Feldhoff, A.; Huber, K.; Wiebcke, M. Rapid room-temperature synthesis and characterization of nanocrystals of a prototypical zeoliticimidazolate framework. Chem. Mater. 2009, 21, 1410–1412.

    Article  Google Scholar 

  36. Li, Y. S.; Bux, H.; Feldhoff, A.; Li, G. L.; Yang, W. S.; Caro, J. Controllable synthesis of metal-organic frameworks: From MOFnanorods to oriented MOF membranes. Adv. Mater. 2010, 22, 3322–3326.

    Article  Google Scholar 

  37. Sindoro, M.; Yanai, N.; Jee, A. Y.; Granick, S. Colloidalsized metal-organic frameworks: Synthesis and applications. Acc. Chem. Res. 2014, 47, 459–469.

    Article  Google Scholar 

  38. Wu, Y. E.; Wang, D. S.; Li, Y. D. Understanding of the major reactions in solution synthesis of functional nanomaterials. Sci. China Mater. 2016, 59, 938–996.

    Article  Google Scholar 

  39. Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.; Bordiga, S.; Lillerud, K. P. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. J. Am. Chem. Soc. 2008, 130, 13850–13851.

    Article  Google Scholar 

  40. Garibay, S. J.; Cohen, S. M. Isoreticular synthesis and modification of frameworks with the UiO-66 topology. Chem. Commun. 2010, 46, 7700–7702.

    Article  Google Scholar 

  41. Wißmann, G.; Schaate, A.; Lilienthal, S.; Bremer, I.; Schneider, A. M.; Behrens, P. Modulated synthesis of Zr-fumarate MOF. Micropor. Mesopor. Mater. 2012, 152, 64–70.

    Article  Google Scholar 

  42. Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O'Keeffe, M.; Yaghi, O. M. High-throughput synthesis of zeoliticimidazolate frameworks and application to CO2 capture. Science 2008, 319, 939–943.

    Article  Google Scholar 

  43. Jiang, H. L.; Liu, B.; Akita, T.; Haruta, M.; Sakurai, H.; Xu, Q. Au@ZIF-8: CO oxidation over gold nanoparticles deposited to metal-organic framework. J. Am. Chem. Soc. 2009, 131, 11302–11303.

    Article  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21641005, 21604038), the Beijing Engineering Center for Hierarchical Catalysts, the Program for Changjiang Scholars and Innovative Research Team in University (No.IRT1205), the Jiangsu Provincial Founds for Natural Science Foundation (No.BK20160975), the Program for Outstanding Young Scholars from the Organization Department of the CPC Central Committee, and the National Basic Research Program of China (973 Program) (Nos. 2014CB932104 and 2015CB932200).

Author information

Authors and Affiliations

  1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Bingqing Wang, Wenxian Liu & Junfeng Liu

  2. Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (Nanjing Tech), Nanjing, 211816, China

    Weina Zhang

Authors
  1. Bingqing Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wenxian Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Weina Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Junfeng Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Junfeng Liu.

Electronic supplementary material

12274_2017_1595_MOESM1_ESM.pdf

Nanoparticles@nanoscale metal-organic framework composites as highly efficient heterogeneous catalysts for size- and shape-selective reactions

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, B., Liu, W., Zhang, W. et al. Nanoparticles@nanoscale metal-organic framework composites as highly efficient heterogeneous catalysts for size- and shape-selective reactions. Nano Res. 10, 3826–3835 (2017). https://doi.org/10.1007/s12274-017-1595-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-017-1595-2

Keywords

Search

Navigation