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Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation

Nature Chemistry volume 4, pages 310–316 (2012)Cite this article

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Abstract

Microporous metal–organic frameworks (MOFs) that display permanent porosity show great promise for a myriad of purposes. The potential applications of MOFs can be developed further and extended by encapsulating various functional species (for example, nanoparticles) within the frameworks. However, despite increasing numbers of reports of nanoparticle/MOF composites, simultaneously to control the size, composition, dispersed nature, spatial distribution and confinement of the incorporated nanoparticles within MOF matrices remains a significant challenge. Here, we report a controlled encapsulation strategy that enables surfactant-capped nanostructured objects of various sizes, shapes and compositions to be enshrouded by a zeolitic imidazolate framework (ZIF-8). The incorporated nanoparticles are well dispersed and fully confined within the ZIF-8 crystals. This strategy also allows the controlled incorporation of multiple nanoparticles within each ZIF-8 crystallite. The as-prepared nanoparticle/ZIF-8 composites exhibit active (catalytic, magnetic and optical) properties that derive from the nanoparticles as well as molecular sieving and orientation effects that originate from the framework material.

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Figure 1: Scheme of the controlled encapsulation of nanoparticles in ZIF-8 crystals.
Figure 2: TEM analysis and UV-vis absorption spectroscopy measurements of the encapsulation of 13 nm Au nanoparticles in ZIF-8 crystals.
Figure 3: TEM images of nanoparticle/ZIF-8 composites that contain different types of nanoparticles.
Figure 4: Gas-sorption data for ZIF-8 and nanoparticle/ZIF-8 composites.
Figure 5: Catalytic, magnetic and photoluminescence properties of nanoparticle/ZIF-8 composites.

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Acknowledgements

F.H. acknowledges financial support from Nanyang Technological University (start-up grant), the AcRF Tier 1 (RG 42/10) from the Ministry of Education, Singapore, and the Singapore National Research Foundation under the Campus for Research Excellence and Technological Enterprise programme Nanomaterials for Energy and Water Management. The Northwestern group acknowledges financial support from the Air Force Office of Scientific Research and Defense Threat Reduction Agency (grant no. HDTRA-09-1-0007). We thank J. Wang and L. You for the measurement of magnetization curves. We thank Y.M. Lam and J.Y. Lek for the gift of CdSe nanoparticles.

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Authors and Affiliations

  1. School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore

    Guang Lu, Shaozhou Li, Xiaoying Qi, Hua Zhang, Qichun Zhang, Xiaodong Chen, Jan Ma, Say Chye Joachim Loo & Fengwei Huo

  2. School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore, 637459, Singapore

    Zhen Guo, Yi Wang, Xin Wang & Yanhui Yang

  3. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Illinois, 60208, Evanston, USA

    Omar K. Farha, Brad G. Hauser & Joseph T. Hupp

  4. Department of Chemistry, National University of Singapore, Singapore, 117543, Singapore

    Sanyang Han & Xiaogang Liu

  5. Institute of Materials Research and Engineering, 3 Research Link, Singapore, 117602, Singapore

    Xiaogang Liu

  6. Department of Chemistry and Center for Nanostructured Electronic Materials, University of Florida, Gainesville, 32611, Florida, USA

    Joseph S. DuChene & Wei D. Wei

  7. Solar Fuels Laboratory, Nanyang Technological University, Singapore, 639798, Singapore

    Say Chye Joachim Loo

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  1. Guang Lu
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Contributions

G.L. conceived the idea, designed and performed the experiments, analysed the results and co-drafted the manuscript. S.L. was primarily responsible for the TEM characterization. Z.G. and Y.Y. designed and performed the catalysis experiments. B.G.H., Y.W. and X.W. assisted with gas-sorption studies. X.Q. and H.Z. synthesized magnetic nanoparticles. S.H. and X.L. carried out the synthesis of upconversion nanocrystals and luminescence analysis of the corresponding composite materials. J.T.H. and O.K.F. contributed to the general methodology, assisted with data interpretation and reviewed the manuscript. F.H. supervised the project, helped design the experiments and co-drafted the manuscript. All authors contributed to the analysis of the manuscript.

Corresponding authors

Correspondence to Joseph T. Hupp or Fengwei Huo.

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Lu, G., Li, S., Guo, Z. et al. Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation. Nature Chem 4, 310–316 (2012). https://doi.org/10.1038/nchem.1272

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