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Surface nano-architecture of a metal–organic framework

Nature Materials volume 9, pages 565–571 (2010)Cite this article

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Abstract

The rational assembly of ultrathin films of metal–organic frameworks (MOFs)—highly ordered microporous materials1,2,3,4,5—with well-controlled growth direction and film thickness is a critical and as yet unrealized issue for enabling the use of MOFs in nanotechnological devices, such as sensors, catalysts and electrodes for fuel cells. Here we report the facile bottom-up fabrication at ambient temperature of such a perfect preferentially oriented MOF nanofilm on a solid surface (NAFS-1), consisting of metalloporphyrin building units. The construction of NAFS-1 was achieved by the unconventional integration in a modular fashion of a layer-by-layer growth technique coupled with the Langmuir–Blodgett method. NAFS-1 is endowed with highly crystalline order both in the out-of-plane and in-plane orientations to the substrate, as demonstrated by synchrotron X-ray surface crystallography. The proposed structural model incorporates metal-coordinated pyridine molecules projected from the two-dimensional sheets that allow each further layer to dock in a highly ordered interdigitated manner in the growth of NAFS-1. We expect that the versatility of the solution-based growth strategy presented here will allow the fabrication of various well-ordered MOF nanofilms, opening the way for their use in a range of important applications.

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Figure 1: Schematic illustration of the fabrication method of NAFS-1.
Figure 2: Layer-by-layer film growth of NAFS-1 followed by ultraviolet–visible absorption spectroscopy.
Figure 3: Out-of-plane synchrotron XRD patterns of NAFS-1.
Figure 4: In-plane synchrotron XRD patterns and the derived structural model for NAFS-1.

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Acknowledgements

We thank JST (CREST), NEDO and JSPS (No. 20350030 and 20655030) and the Global COE Program ‘Science for Future Molecular Systems’ for financial support, SPring-8 for access to the synchrotron X-ray facilities under the Priority Nanotechnology Support Program administered by JASRI (2008B1801, 2009A1703) and under proposal 2008B2205 and the Center of Advanced Instrumental Analysis, Kyushu University for the use of the FT-IR spectrometer and the ESCA system.

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  1. Rie Makiura

    Present address: Present address: Nanoscience and Nanotechnology Research Center, Osaka Prefecture University, Gakuencho 1-2, Naka-ku, Sakai, Osaka 599-8570, Japan,

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Kyushu University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-8581, Japan

    Rie Makiura, Soichiro Motoyama & Hiroshi Kitagawa

  2. CREST, Japan Science and Technology Agency, Sanbancho 5, Chiyoda-ku, Tokyo 102-0075, Japan

    Rie Makiura, Hiroaki Yamanaka, Osami Sakata & Hiroshi Kitagawa

  3. Department of Applied Chemistry, National Defense Academy, Yokosuka, Kanagawa 239-8686, Japan

    Yasushi Umemura

  4. Japan Synchrotron Radiation Research Institute, Kouto 1-1-1, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan

    Hiroaki Yamanaka & Osami Sakata

  5. Division of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan

    Hiroshi Kitagawa

  6. INAMORI Frontier Research Center, Kyushu University, Motooka 744, Nishi-ku, Fukuoka 819-3095, Japan

    Hiroshi Kitagawa

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Contributions

This work has been carried out mainly by JST-CREST and METI-NEDO projects where H.K. is a project leader and responsible for all. R.M. designed this study, interpreted the results and carried out sample preparation, XPS, infrared and AFM characterization and structural model construction. R.M. and Y.U. carried out Langmuir–Blodgett film fabrication and absorption spectra measurements. O.S. was responsible for supervising the synchrotron XRD measurements. R.M. carried out the synchrotron XRD measurements with the help of S.M. and H.Y. All authors commented on the manuscript. R.M and H.K. were responsible for writing the manuscript.

Corresponding authors

Correspondence to Rie Makiura or Hiroshi Kitagawa.

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The authors declare no competing financial interests.

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Makiura, R., Motoyama, S., Umemura, Y. et al. Surface nano-architecture of a metal–organic framework. Nature Mater 9, 565–571 (2010). https://doi.org/10.1038/nmat2769

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