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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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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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.
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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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DOI: https://doi.org/10.1038/nmat2769
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