An Ultrahydrophobic Fluorous Metal–Organic Framework Derived Recyclable Composite as a Promising Platform to Tackle Marine Oil Spills

Mukherjee, Soumya; Kansara, Ankit M.; Saha, Debasis; Gonnade, Rajesh G.; Mullangi, Dinesh; Manna, Biplab; Desai, Aamod V.; Thorat, Shridhar H.; Singh, Puyam S.; Mukherjee, Arnab; Ghosh, Sujit K.

doi:10.1002/chem.201601724

Cited by 106 publications

(71 citation statements)

References 85 publications

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“…The as-synthesized sample included guest H 2 O molecules in the other hydrophilic channels but the desolvated form selectively took in hydrophobic heptane guests within its CF 3 -decorated channels. Ghosh and colleagues 14 found that the desolvated form of the two-dimensional MOF, {[Cu 4 (L3) 4 …”

Section: Mofs Containing Fluorine-and Trifluoromethyl-substituted Orgmentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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Fluorine, the element with the highest electronegativity and low electric polarizability, can produce a variety of characteristics, including specific adsorption sites for molecules as well as flexibility to the host materials. In this review, we will introduce fluorine-functionalized metal-organic frameworks/porous coordination polymers that show unique and unprecedented structures, structural transformations, and gas and vapor adsorption/separation properties derived from the fluorine characteristics. NPG Asia Materials (2017) 9, e433; doi:10.1038/am.2017.165; published online 29 September 2017 INTRODUCTIONDuring the last two decades, metal-organic frameworks (MOFs)/ porous coordination polymers (PCPs) composed of metal ions and organic bridging ligands as main building units and, in some cases, inorganic ligands, have been investigated extensively because of their versatile structural diversity, high structural controllability (pore size, shape, dimension, flexibility and surface environment), high crystallinity, and their potential porous properties/functionalities in a variety of research fields such as storage and separation, catalysis, drug delivery and sensing ability. 1-3 The porous properties of MOFs/PCPs can be finely tailored by not only chemical modification of organic ligands and judicious choice of components but also a variety of techniques such as solid solution formation, defect engineering, core-shell structure, crystal morphology and size control, and so on. For example, the appropriate combination of organic bridging ligands provided the Zn(II) MOF, [Zn 4 O(bte) 4/3 (bpdc)] (bte = 4,4′,4′′-[benzene-1,3,5-triyl-tris (ethyne-2,1-diyl)]tribenzoate, bpdc = biphenyl-4,4′-dicarboxylate), with ultra-high Brunauer-Emmett-Teller and Langmuir specific surface areas close to 6000 and 10 000 m 2 g − 1 , respectively. 4 Unlike porous inorganic zeolites and porous carbon materials, MOFs often give flexible structures. As coordination bonds, hydrogen bonds and van der Waals interactions that are used to assemble each component are weaker (bonding energies are 10~200 kJ mol − 1 ) than covalent and ionic bonds (200~1000 kJ mol − 1 ), reversible rotation, bending and breaking of these weaker bonds easily occurs, resulting in structural changes. One representative of flexible MOFs is [Cr(OH)(1,4-bdc)] (MIL-53(Cr), 1,4-bdc = 1,4-benzenedicarboxylate), in which local reorientation of the coordination bond triggered by guest adsorption/ desorption induced the structural transformation between narrow pore and large pore forms. 5 In addition, many MOFs show high crystallinity as with porous inorganic zeolites, which is advantageous for understanding deeply the structure-property relationship using single-crystal and powder X-ray diffraction techniques. For example, the unprecedented highly selective CO sorption from a CO/N 2 mixture, which is

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Section: Mofs Containing Fluorine-and Trifluoromethyl-substituted Orgmentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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“…To construct stable waterproof MOFs without the propensity to undergo degradation in the presence of moisture, a common approach is to introduce hydrophobic moieties into the framework or onto the crystal surface, either through de novo synthesis or through postsynthetic modification (PSM) . This kind of approach mainly focuses on lowering the surface free energy.…”

Section: Introductionmentioning

confidence: 99%

Self‐Generation of Surface Roughness by Low‐Surface‐Energy Alkyl Chains for Highly Stable Superhydrophobic/Superoleophilic MOFs with Multiple Functionalities

et al. 2019

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We transformed the hydrophilic metal–organic framework (MOF) UiO‐67 into hydrophobic UiO‐67‐Rs (R=alkyl) by introducing alkyl chains into organic linkers, which not only protected hydrophilic Zr6O8 clusters to make the MOF interspace superoleophilic, but also led to a rough crystal surface beneficial for superhydrophobicity. The UiO‐67‐Rs displayed high acid, base, and water stability, and long alkyl chains offered better hydrophobicity. Good hydrophobicity/oleophilicity were also possible with mixed‐ligand MOFs containing metal‐binding ligands. Thus, a (super)hydrophobic MOF catalyst loaded with Pd centers efficiently catalyzed Sonogashira reactions in water at ambient temperature. Studies of the hydrophobic effects of the coordination interspace and the outer surface suggest a simple de novo strategy for the synthesis of superhydrophobic MOFs that combine surface roughness and low surface energy. Such MOFs have potential for environmentally friendly catalysis and water purification.

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“…[21][22][23][24][25][26][27][28] A great effort has been dedicated to fabricating porous materials with hierarchical porosity with a large specific surface area and being water resistant. Stable hydrophobic MOFs were prepared using hydrophobic functional (F and alkyl) organic linkers or through postsynthetic modification of MOF using hydrophobic groups; although, one cannot rely on many typical MOFs for the oil adsorption due to their microchannels.…”

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confidence: 99%

Shape Controlled Hierarchical Porous Hydrophobic/Oleophilic Metal‐Organic Nanofibrous Gel Composites for Oil Adsorption

et al. 2017

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An Ultrahydrophobic Fluorous Metal–Organic Framework Derived Recyclable Composite as a Promising Platform to Tackle Marine Oil Spills

Cited by 106 publications

References 85 publications

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

Self‐Generation of Surface Roughness by Low‐Surface‐Energy Alkyl Chains for Highly Stable Superhydrophobic/Superoleophilic MOFs with Multiple Functionalities

Shape Controlled Hierarchical Porous Hydrophobic/Oleophilic Metal‐Organic Nanofibrous Gel Composites for Oil Adsorption

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