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Metal–organic framework nanosheets in polymer composite materials for gas separation

Nature Materials volume 14, pages 48–55 (2015)Cite this article

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Abstract

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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Figure 1: Synthesis and structure of the metal–organic framework nanostructures.
Figure 2: Versatility and scope of the three-layer synthesis strategy to produce 2D MOF nanocrystals.
Figure 3: Sorption properties of CuBDC MOF crystals.
Figure 4: Tomographic FIB–SEM analysis of MOF–polymer composite membranes.
Figure 5: Image analysis of FIB–SEM tomograms for MOF–polymer composite membranes.
Figure 6: Application of the MOF–polymer composites in a gas separation process.

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Acknowledgements

The Kavli Institute of Nanoscience (TUDelft) and the Microscopy Service of the Polytechnic University of Valencia (UPV) are acknowledged for access to their microscopy facilities. P. Alkemade (TUDelft) and J.L. Moya (UPV) are acknowledged for their guidance and assistance in the acquisition of FIB–SEM data sets. The research leading to these results has received funding (J.G., B.S.) from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement no. 335746, CrystEng-MOF-MMM. T.R. is grateful to TUDelft for funding. G.P. acknowledges the A. von Humboldt Foundation for a research grant. A.C., I.L. and F.X.L.i.X. thank Consolider-Ingenio 2010 (project MULTICAT) and the ‘Severo Ochoa’ programme for support. I.L. also thanks CSIC for a JAE doctoral grant.

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Author notes

  1. Tania Rodenas, Ignacio Luz and Gonzalo Prieto: These authors contributed equally to this work.

Authors and Affiliations

  1. Catalysis Engineering, ChemE, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands

    Tania Rodenas, Beatriz Seoane, Freek Kapteijn & Jorge Gascon

  2. Instituto de Tecnología Química CSIC-UPV, Universidad Politécnica de Valencia, Consejo Superior de Investigaciones Científicas, Avenida de los Naranjos, s/n, 46022 Valencia, Spain

    Ignacio Luz, Avelino Corma & Francesc X. Llabrés i Xamena

  3. Max Planck Institut für Kohlenforschung, Kaiser Wilhelm Platz 1 45470 Mülheim an der Ruhr, Germany,

    Gonzalo Prieto

  4. Kavli Institute of Nanoscience, Delft University of Technology, Lorentzweg 1, 2628 CJ Delft, The Netherlands

    Hozanna Miro

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Contributions

A.C., F.K., F.X.L.i.X. and J.G. conceived the research. F.X.L.i.X. and J.G. designed the experiments and coordinated the research. I.L. synthesized and characterized the MOF materials. T.R. and B.S. synthesized and characterized the MOF–polymer composites. H.M. and T.R. recorded the FIB–SEM data sets. G.P. contributed conception and execution of FIB–SEM data reconstruction and image analysis, with the assistance of T.R. All authors contributed to analysis and discussion on the data. The manuscript was primarily written by T.R., G.P., F.X.L.i.X. and J.G., with input from all authors.

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Correspondence to Francesc X. Llabrés i Xamena or Jorge Gascon.

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Rodenas, T., Luz, I., Prieto, G. et al. Metal–organic framework nanosheets in polymer composite materials for gas separation. Nature Mater 14, 48–55 (2015). https://doi.org/10.1038/nmat4113

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