Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphic replication

• Published in: Nature materials Vol. 11; no. 8; pp. 717 - 723
• Main Authors: Reboul, Julien, Furukawa, Shuhei, Horike, Nao, Tsotsalas, Manuel, Hirai, Kenji, Uehara, Hiromitsu, Kondo, Mio, Louvain, Nicolas, Sakata, Osami, Kitagawa, Susumu
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 24.06.2012; Nature Publishing Group
• Subjects: 639/301/299/1013; 639/301/923/1028; 639/301/930/1032; Aerogels; Aluminum oxide; Architecture; Biomaterials; Chemical Sciences; Chemistry and Materials Science; Condensed Matter Physics; Coordination polymers; Crystallization; Crystals; Ethanol; Ethyl alcohol; Mass transfer; Materials Science; Mesoclimatology; Metal oxides; Metals; Nanotechnology; Nucleation; Optical and Electronic Materials; Polymers; Porosity; Porous materials; Replication; Separation
• ISSN: 1476-1122; 1476-4660
• DOI: 10.1038/nmat3359

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. The spatial organization of porous coordination-polymer crystals into higher-order structures is critical for their integration in heterogeneous catalysts, separation systems and electrochemical devices. A method for spatially controlling the nucleation site leading to the formation of mesoscopic architecture in porous coordination polymers, in both two and three dimensions, is now demonstrated.