Facile "modular assembly" for fast construction of a highly oriented crystalline MOF nanofilm.

The preparation of crystalline, ordered thin films of metal-organic frameworks (MOFs) will be a critical process for MOF-based nanodevices in the future. MOF thin films with perfect orientation and excellent crystallinity were formed with novel nanosheet-structured components, Cu-TCPP [TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin], by a new "modular assembly" strategy. The modular assembly process involves two steps: a "modularization" step is used to synthesize highly crystalline "modules" with a nanosized structure that can be conveniently assembled into a thin film in the following "assembly" step. With this method, MOF thin films can easily be set up on different substrates at very high speed with controllable thickness. This new approach also enabled us to prepare highly oriented crystalline thin films of MOFs that cannot be prepared in thin-film form by traditional techniques.

[1]  T. Bein,et al.  Oriented growth of the metal organic framework Cu(3)(BTC)(2)(H(2)O)(3).xH(2)O tunable with functionalized self-assembled monolayers. , 2007, Journal of the American Chemical Society.

[2]  M. Carreon,et al.  Highly permeable zeolite imidazolate framework-8 membranes for CO2/CH4 separation. , 2010, Journal of the American Chemical Society.

[3]  O. Shekhah,et al.  Thin films of metal-organic frameworks. , 2009, Chemical Society reviews.

[4]  Jinho Oh,et al.  A homochiral metal–organic porous material for enantioselective separation and catalysis , 2000, Nature.

[5]  C. Hu,et al.  Pillared porphyrin homologous series: intergrowth in metal-organic frameworks. , 2009, Inorganic chemistry.

[6]  Hiroaki Yamanaka,et al.  Surface nano-architecture of a metal-organic framework. , 2010, Nature materials.

[7]  Mircea Dincă,et al.  Hydrogen storage in metal-organic frameworks. , 2009, Chemical Society reviews.

[8]  I. Imaz,et al.  Single-crystal metal-organic framework arrays. , 2011, Journal of the American Chemical Society.

[9]  C. Hu,et al.  Structural Variation in Porphyrin Pillared Homologous Series: Influence of Distinct Coordination Centers for Pillars on Framework Topology , 2009 .

[10]  L. Qiu,et al.  Fabrication of nanosheets of a fluorescent metal–organic framework [Zn(BDC)(H2O)]n (BDC = 1,4-benzenedicarboxylate): Ultrasonic synthesis and sensing of ethylamine , 2008 .

[11]  Jan Fransaer,et al.  Patterned Growth of Metal-Organic Framework Coatings by Electrochemical Synthesis , 2009 .

[12]  Gérard Férey,et al.  Hybrid porous solids: past, present, future. , 2008, Chemical Society reviews.

[13]  Susumu Kitagawa,et al.  Functional porous coordination polymers. , 2004, Angewandte Chemie.

[14]  C. Serre,et al.  A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area , 2005, Science.

[15]  O. Shekhah,et al.  MOF thin films: existing and future applications. , 2011, Chemical Society reviews.

[16]  V. Thangadurai,et al.  Anhydrous proton conduction at 150 °C in a crystalline metal-organic framework. , 2009, Nature chemistry.

[17]  Kenji Sumida,et al.  Carbon dioxide capture in metal-organic frameworks. , 2012, Chemical reviews.

[18]  Jürgen Caro,et al.  Zeolitic imidazolate framework membrane with molecular sieving properties by microwave-assisted solvothermal synthesis. , 2009, Journal of the American Chemical Society.

[19]  O. Shekhah,et al.  Liquid-phase epitaxy of multicomponent layer-based porous coordination polymer thin films of [M(L)(P)0.5] type: importance of deposition sequence on the oriented growth. , 2011, Chemistry.

[20]  L. Francis,et al.  Dispersible Exfoliated Zeolite Nanosheets and Their Application as a Selective Membrane , 2011, Science.

[21]  Michael O'Keeffe,et al.  A route to high surface area, porosity and inclusion of large molecules in crystals , 2004, Nature.

[22]  T. Bein,et al.  Synthesis of well-ordered COF monolayers: surface growth of nanocrystalline precursors versus direct on-surface polycondensation. , 2011, ACS nano.

[23]  M. Kurmoo Magnetic metal-organic frameworks. , 2009, Chemical Society reviews.

[24]  M. Kondo,et al.  MOF-on-MOF heteroepitaxy: perfectly oriented [Zn2(ndc)2(dabco)]n grown on [Cu2(ndc)2(dabco)]n thin films. , 2011, Dalton transactions.

[25]  S. Kitagawa,et al.  Crystal morphology-directed framework orientation in porous coordination polymer films and freestanding membranes via Langmuir–Blodgettry , 2012 .

[26]  Hong-Cai Zhou,et al.  Metal-organic frameworks for separations. , 2012, Chemical reviews.

[27]  R. Fischer,et al.  Metal-organic framework thin films: from fundamentals to applications. , 2012, Chemical reviews.

[28]  S. Kitagawa,et al.  Selective sorption of oxygen and nitric oxide by an electron-donating flexible porous coordination polymer , 2010, Nature Chemistry.

[29]  Richard P Van Duyne,et al.  Metal-organic framework thin film for enhanced localized surface plasmon resonance gas sensing. , 2010, Analytical chemistry.

[30]  C. Wöll,et al.  Chemistry of SURMOFs: layer-selective installation of functional groups and post-synthetic covalent modification probed by fluorescence microscopy. , 2011, Journal of the American Chemical Society.

[31]  T. Do,et al.  Rational Synthesis of Metal–Organic Framework Nanocubes and Nanosheets Using Selective Modulators and Their Morphology-Dependent Gas-Sorption Properties , 2012 .

[32]  Porous Porphyrin Nanoarchitectures on Surfaces , 2010 .

[33]  A Alec Talin,et al.  Stress-induced chemical detection using flexible metal-organic frameworks. , 2008, Journal of the American Chemical Society.

[34]  S. Qiu,et al.  "Twin copper source" growth of metal-organic framework membrane: Cu(3)(BTC)(2) with high permeability and selectivity for recycling H(2). , 2009, Journal of the American Chemical Society.

[35]  S. Mayo,et al.  A new method to position and functionalize metal-organic framework crystals , 2011, Nature communications.

[36]  Osami Sakata,et al.  Highly crystalline nanofilm by layering of porphyrin metal-organic framework sheets. , 2011, Journal of the American Chemical Society.

[37]  A. Fujiwara,et al.  Step-by-step fabrication of a highly oriented crystalline three-dimensional pillared-layer-type metal-organic framework thin film confirmed by synchrotron X-ray diffraction. , 2012, Journal of the American Chemical Society.

[38]  Abraham M. Shultz,et al.  Active-site-accessible, porphyrinic metal-organic framework materials. , 2011, Journal of the American Chemical Society.

[39]  Michael O'Keeffe,et al.  Reticular synthesis and the design of new materials , 2003, Nature.

[40]  Hiroshi Uji-i,et al.  Direct Patterning of Oriented Metal–Organic Framework Crystals via Control over Crystallization Kinetics in Clear Precursor Solutions , 2010, Advanced materials.

[41]  Qiang Xu,et al.  Top-down fabrication of crystalline metal-organic framework nanosheets. , 2011, Chemical communications.

[42]  A. Terfort,et al.  Rapid Room‐Temperature Synthesis of Metal–Organic Framework HKUST‐1 Crystals in Bulk and as Oriented and Patterned Thin Films , 2011 .