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Rapid preparation of flexible porous coordination polymer nanocrystals with accelerated guest adsorption kinetics

Nature Chemistry volume 2, pages 410–416 (2010)Cite this article

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Abstract

Porous coordination polymers, in particular flexible porous coordination polymer networks that change their network structure on guest adsorption, have enormous potential in applications involving selective storage, separation and sensing. Despite the expected significant differences in their adsorption properties, porous coordination polymer nanocrystals remain largely unexplored, and there have been no reports about studies on flexible porous coordination polymer nanocrystals, mainly due to a lack of preparation methods. Here, we present a new technique for the rapid preparation of porous coordination polymer nanocrystals that combines non-aqueous inverse microemulsion with ultrasonication. Uniform nanocrystals of {[Zn(ip)(bpy)]}n (ip = isophthalate, bpy = 4,4′-bipyridyl; CID-1), a flexible porous coordination polymer, have been prepared by this method and analysed using field-emission scanning electron microscopy, energy-dispersive X-ray analysis, infrared spectroscopy, Raman spectroscopy and X-ray powder diffraction. A model for particle formation and growth is presented and discussed. Adsorption experiments with methanol show that the overall adsorption capacities of nanoparticles and bulk are almost identical, but the shapes of the sorption isotherms differ significantly and the adsorption kinetics increase dramatically.

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Figure 1: Schematic of CID-1 and FE-SEM images of coordination compounds obtained by various reaction processes.
Figure 2: FE-SEM images of NCID-1b–g.
Figure 3: XRPD patterns of bulk-CID-1 and NCID-1a in different states.
Figure 4: Model for PCP nanoparticle formation and growth.
Figure 5: Gas adsorption properties of bulk-CID-1 and NCID-1a.

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Acknowledgements

The authors thank R. Matsuda, H. Sato and H. Sakamoto for their guidance with XRPD measurements, S. Singh, S. Furukawa and T. Tsuruoka for helpful discussions, and N. Yanai for his practical help. Thanks also go to S. Ruetten and K.H. Phan for their kind help with the measurements for FE-SEM, W. Richtering for experimental support regarding dynamic light scattering, and W. Tillmann for carrying out the IR and Raman spectrum measurements. This work was supported by the Exploratory Research for Advanced Technology (ERATO) ‘Kitagawa Integrated Pore Project’ of the Japan Society and Technology Agency (JST).

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Authors and Affiliations

  1. DWI e.V. and Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Pauwelsstrasse 8, Aachen, 52056, Germany

    Daisuke Tanaka, Artur Henke, Krystyna Albrecht, Martin Moeller & Juergen Groll

  2. Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan

    Keiji Nakagawa & Susumu Kitagawa

  3. Institute for Integrated Cell-Material Sciences, Kyoto University Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan

    Susumu Kitagawa

  4. Kitagawa Integrated Pore Project, Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology Agency (JST) Kyoto Research Park, 134, Chudoji Minami-machi, Shimogyo-ku, Kyoto, 600-8813, Japan

    Susumu Kitagawa

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  1. Daisuke Tanaka
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Contributions

D.T., S.K. and J.G. conceived and designed the experiments. D.T., A.H. and K.N. performed the experiments. D.T., A.H., K.N., K.A. and J.G. analysed the data. D.T., A.H., K.A., M.M., S.K. and J.G. contributed to writing the paper. All authors contributed to the optimization of the experiments.

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Correspondence to Susumu Kitagawa or Juergen Groll.

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Tanaka, D., Henke, A., Albrecht, K. et al. Rapid preparation of flexible porous coordination polymer nanocrystals with accelerated guest adsorption kinetics. Nature Chem 2, 410–416 (2010). https://doi.org/10.1038/nchem.627

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