4.8 Article

Nanoporous Transparent MOF Glasses with Accessible Internal Surface

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 34, Pages 10818-10821

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b07078

Keywords

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Funding

  1. Office of Science, Office of Basic Energy Sciences, U.S. Department of Energy [DE-AC02- 05CH11231]
  2. U.S. Department of Energy [DE-AC02-05CH11231, 6920968]
  3. BASF SE (Ludwigshafen, Germany)
  4. King Abdulaziz City for Science and Technology (Riyadh, Saudi Arabia)
  5. Suzhou Industrial Park fellowship

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While glassy materials can be made from virtually every class of liquid (metallic, molecular, covalent, and ionic), to date, formation of glasses in which structural units impart porosity on the nanoscopic level remains Undeveloped. In view of the well-established porosity of metal organic frameworks (MOFs) and the flexibility of 'their design, we have sought to combine their formation principles with the general versatility of glassy materials. Although the preparation of glassy MOFs can be achieved by amorphization 'of crystalline frameworks, transparent glassy MOFs exhibiting permanent porosity accessible to gases are yet to be reported. Here, we present a generalizable chemical strategy for making such MOF glasses by assembly from viscous solutions of metal node and organic strut and subsequent evaporation of a plasticizer modulator solvent. This process yields glasses With 300 m(2)/g internal surface area (obtained' from N-2 adsorption isotherms) and a 2 nm pore pore separation. On a volumetric basis, this porosity (0.33 cm(3)/cm(3)) is 3 times that of the early MOFs (0.11 cm(3)/cm(3) for MOF-2) and within range of the most porous MOFs known (0.60 cm(3)/cm(3) for MOF-5). We believe the porosity originates from a 3D covalent network as evidenced by the disappearance-of the glass transition signature as the solvent is removed and the highly cross-linked nanostructure builds up. Our work represents an important step forward in translating the versatility and porosity of MOFs to glassy materials.

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