4.6 Article

Conformal and highly adsorptive metal-organic framework thin films via layer-by-layer growth on ALD-coated fiber mats

Journal

JOURNAL OF MATERIALS CHEMISTRY A
Volume 3, Issue 4, Pages 1458-1464

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c4ta05501b

Keywords

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Funding

  1. ECBC [W911SR-07-C-0075]
  2. Joint Science and Technology Office through Army Research Office [W911NF-13-1-0173]
  3. State of North Carolina
  4. National Science Foundation

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Integration of metal-organic frameworks (MOFs) on textiles shows promise for enabling facile deployment and expanding MOF applications. While MOFs deposited on flat substrates can show relatively smooth surface texture, most previous reports of MOFs integrated on fibers show poor conformality with many individual crystal domains. Here we report a new low-temperature (<70 degrees C) method to deposit uniform and smooth MOF thin films on fiber surfaces using an energy enhanced layer-by-layer (LbL) method with an ALD Al2O3 nucleation layer. Cross-sectional TEM images show a well-defined core@shell structure of the MOF-functionalized fiber, and SEM shows a flat MOF surface texture. We analyze the thickness and mass increase data of LbL HKUST-1 MOF thin films on ALD-coated polypropylene fibers and find the growth rate to be 288-290 ng cm(-2) per LbL cycle. Unlike planar LbL MOF embodiments where adsorption capacities are difficult to quantify, the large volume quantity on a typical fiber mat enables accurate surface area measurement of these unique MOF morphologies. After 40 LbL cycles the MOFs on fibers exhibit N-2 adsorption BET surface areas of up to 93.6 m(2) g(MOF+fiber)(-1) (similar to 535 m(2) g(MOF)(-1)) and breakthrough test results reveal high dynamic loadings for NH3 (1.37 molNH(3) kg(MOF+fiber)(-1)) and H2S (1.49 molH(2)S kg(MOF+fiber)(-1)). This synthesis route is applicable to many polymer fibers, and the fiber@ALD@MOF structure is promising for gas filtration, membrane separation, catalysis, chemical sensing and other applications.

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