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Centimetre-scale micropore alignment in oriented polycrystalline metal–organic framework films via heteroepitaxial growth

Nature Materials volume 16, pages 342–348 (2017)Cite this article

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Abstract

The fabrication of oriented, crystalline films of metal–organic frameworks (MOFs) is a critical step toward their application to advanced technologies such as optics, microelectronics, microfluidics and sensing. However, the direct synthesis of MOF films with controlled crystalline orientation remains a significant challenge. Here we report a one-step approach, carried out under mild conditions, that exploits heteroepitaxial growth for the rapid fabrication of oriented polycrystalline MOF films on the centimetre scale. Our methodology employs crystalline copper hydroxide as a substrate and yields MOF films with oriented pore channels on scales that primarily depend on the dimensions of the substrate. To demonstrate that an anisotropic crystalline morphology can translate to a functional property, we assembled a centimetre-scale MOF film in the presence of a dye and showed that the optical response could be switched ‘ON’ or ‘OFF’ by simply rotating the film.

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Figure 1: Approach to fully oriented MOF growth.
Figure 2: Heteroepitaxially grown Cu2(BDC)2 on vertically oriented Cu(OH)2 nanotubes.
Figure 3: Micrographs and X-ray diffraction patterns of the macroscopically oriented MOF films.
Figure 4: Switching of fluorescence of dye, DMASP, by a polarization of an incident light.

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Acknowledgements

This work was partly supported by a Grant-in-Aid for Scientific Research (B) (26288108), a Grant-in-Aid for Scientific Research on Innovative Area (26630322) from the Ministry of Education, Culture Sports, Science and Technology of Japan, and the Strategic Young Researcher Overseas Visits Program for Accelerating Brain Circulation from Japan Society of Promotion of Science. K.O. acknowledges JSPS Research Fellowship for Young Scientists. We acknowledge the use of facilities within the Monash Centre for Electron Microscopy. This research used equipment funded by the Australian Research Council grant LE110100223. P.F. acknowledges the Australian Research Council (DE120102451) and the ASTE JSPS schemes (Australia Japan Emerging Research Leaders Exchange and Invitation Fellowship programs). T.D.C. is acknowledged for helpful discussions. C.D. would like to acknowledge the JSPS for the visiting professorial fellowship. R. Makiura is acknowledged for helpful discussion and reference sample preparations.

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Authors and Affiliations

  1. Graz University of Technology, Institute of Physical and Theoretical Chemistry, Stremayrgasse 9/Z2, 8010 Graz, Austria

    Paolo Falcaro

  2. Future Industries, CSIRO, Private Bag 10, Clayton South, MDC, Victoria 3169, Australia

    Paolo Falcaro, Aaron W. Thornton & Anita J. Hill

  3. International Institute for Nano/Meso Materials Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan

    Paolo Falcaro, Yasuaki Tokudome & Masahide Takahashi

  4. Department of Chemistry, The University of Adelaide, Adelaide, South Australia 5005, Australia

    Paolo Falcaro & Christian Doonan

  5. Department of Materials Science, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan

    Kenji Okada, Takaaki Hara, Ken Ikigaki, Yasuaki Tokudome & Masahide Takahashi

  6. Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan

    Kenji Okada

  7. Monash Centre for Electron Microscopy, Monash University, Victoria 3800, Australia

    Timothy Williams

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Contributions

P.F. and M.T. conceived, designed and supervised the project with the help of A.H. and C.D.; K.O., T.H., K.I. and Y.T. performed the sample preparations, experiments and analysed the data; T.W., P.F. and M.T. performed TEM observations and analysed the results; A.W.T. performed the computational study of molecular simulations; P.F., K.O., C.D. and M.T. co-wrote the paper.

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Correspondence to Paolo Falcaro or Masahide Takahashi.

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Falcaro, P., Okada, K., Hara, T. et al. Centimetre-scale micropore alignment in oriented polycrystalline metal–organic framework films via heteroepitaxial growth. Nature Mater 16, 342–348 (2017). https://doi.org/10.1038/nmat4815

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