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Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphic replication

Abstract

The spatial organization of porous coordination polymer (PCP) crystals into higher-order structures is critical for their integration into separation systems, heterogeneous catalysts, ion/electron transport and photonic devices. Here, we demonstrate a rapid method to spatially control the nucleation site, leading to the formation of mesoscopic architecture made of PCPs, in both two and three dimensions. Inspired by geological processes, this method relies on the morphological replacement of a shaped sacrificial metal oxide used both as a metal source and as an ‘architecture-directing agent’ by an analogous PCP architecture. Spatiotemporal harmonization of the metal oxide dissolution and the PCP crystallization allowed the preservation of very fine mineral morphological details of periodic alumina inverse opal structures. The replication of randomly structured alumina aerogels resulted in a PCP architecture with hierarchical porosity in which the hydrophobic micropores of the PCP and the mesopores/macropores inherited from the parent aerogels synergistically enhanced the material’s selectivity and mass transfer for water/ethanol separation.

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Figure 1: The coordination replication and mesoscopic architecture concept.
Figure 2: Coordination replication to form two- and three-dimensional mesoscopic architectures based on a porous aluminium coordination polymer.
Figure 3: Time-course monitoring of the coordination replication by FESEM.
Figure 4: Schematic view of the coordination replication mechanism.
Figure 5: Replication of randomly structured alumina aerogels for the formation of mesoscopic PCP architectures used as water/ethanol separation systems.
Figure 6: Water/ethanol separation with the mesoscopic PCP architecture, Meso-PCP or Macro-PCP.

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Acknowledgements

The authors thank N. Morone, the support from CeMI, and T. Tsuruoka for assistance with measurement for FESEM and K. Shiomi for assistance with breakthrough experiments. iCeMS is supported by World Premier International Research Initiative, MEXT, Japan.

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Contributions

S.F., J.R. and S.K. conceived and designed the experiments. J.R., N.H. and M.T. performed all synthetic and characterization experiments. S.F., K.H., H.U., M.K., N.L. and O.S. carried out synchrotron X-ray diffraction measurements. J.R. carried out water/ethanol separation experiments. J.R. and S.F. analysed the data and co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Shuhei Furukawa or Susumu Kitagawa.

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The authors declare no competing financial interests.

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Reboul, J., Furukawa, S., Horike, N. et al. Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphic replication. Nature Mater 11, 717–723 (2012). https://doi.org/10.1038/nmat3359

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