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Nat Mater. 2015 Jan;14(1):48-55. doi: 10.1038/nmat4113. Epub 2014 Nov 2.

Metal-organic framework nanosheets in polymer composite materials for gas separation.

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Catalysis Engineering, ChemE, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
Instituto de Tecnología Química CSIC-UPV, Universidad Politécnica de Valencia, Consejo Superior de Investigaciones Científicas, Av. de los Naranjos, s/n, 46022 Valencia, Spain.
Max Planck Institut für Kohlenforschung, Kaiser Wilhelm Platz 1, 45470 Mülheim an der Ruhr, Germany.
Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft, The Netherlands.
Contributed equally


Composites incorporating two-dimensional nanostructures within polymeric matrices have potential as functional components for several technologies, including gas separation. Prospectively, employing metal-organic frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of freestanding nanosheets has proved challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometre lateral dimensions and nanometre thickness. Incorporating MOF nanosheets into polymer matrices endows the resultant composites with outstanding CO2 separation performance from CO2/CH4 gas mixtures, together with an unusual and highly desired increase in the separation selectivity with pressure. As revealed by tomographic focused ion beam scanning electron microscopy, the unique separation behaviour stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared with isotropic crystals, which improves the efficiency of molecular discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications.

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