Metal–organic frameworks based on octafluorobiphenyl-4,4′-dicarboxylate: synthesis, crystal structure, and surface functionality

Cheplakova, Anastasia M.; Kovalenko, Konstantin A.; Самсоненко, Д. Г.; Лазаренко, В. А.; Khrustalev, Victor N.; Vinogradov, A. S.; Карпов, В. М.; Platonov, V. Е.; Fedin, Vladimir P.

doi:10.1039/c7dt04566b

Cited by 32 publications

(12 citation statements)

References 43 publications

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“…This review offers a comprehensive overview of the state of the art in hydrophobic MOF synthesis and the field's challenges and opportunities. Various synthetic strategies for preparing hydrophobic MOFs and their composites are introduced . We discuss the basics of wetting and critical challenges in the characterization of these hydrophobic materials.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobic Metal–Organic Frameworks

et al. 2019

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formed from organic ligands and metal cations. [1][2][3][4][5][6][7][8][9][10] They are typically synthesized under mild conditions via coordinationdirected self-assembly processes and are also known as metal-organic coordination networks and porous coordination polymers. [11][12][13][14] Due to their high surface areas, large porosity, tunable pore sizes, and functionalities, MOFs have prospective applications in fields such as gas storage/separation, sensing or recognition, proton conduction, and magnetism. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] However, the advantageous unique structural features of even some of the best-performing MOFs are readily degraded because of their high moisture sensitivity, which may limit their practical applications. [29][30][31][32] Consequently, there is an ongoing search for highly hydrophobic, porous, sorbent materials to be employed in various large-scale applications in industry such as oil spill cleanup, hydrocarbon storage/separation, or water purification. [33][34][35][36][37] Many academics, industrial scientists, and engineers have therefore conducted research on the fabrication of superhydrophobic surfaces, which involves hydrophobic surface modification and creating surface roughness on the micrometer-or nanoscale. Hydrophobic surfaces are defined as substrates with an apparent contact angle greater than 90° with respect to water. On superhydrophobic materials, water droplets have contact angles above 150° and show very low adhesion because the drops partially rest on an air cushion. The surface energy and roughness govern the wettability of hydrophobic surfaces. In general, lower surface energies and higher roughness are associated with larger contact angles, lower contact angle hysteresis, and robust superhydrophobicity. Because of their ultralow surface energies (10-20 mN m −1 ), alkyl-based or fluorinated compounds are commonly used as hydrophobic modifiers to prepare surfaces with high intrinsic contact angles (>90°). [33][34][35][36][37][38][39][40][41][42] Recently, few methods have been developed for synthesizing hydrophobic MOFs including both pristine and composite systems. This review offers a comprehensive overview of the state of the art in hydrophobic MOF synthesis and the field's challenges and opportunities. Various synthetic strategies for preparing hydrophobic MOFs and their composites are introduced. We discuss the basics of wetting and critical challenges in the characterization of these hydrophobic materials. The potential applications of hydrophobic MOFs and related Metal-organic frameworks (MOFs) have diverse potential applications in catalysis, gas storage, separation, and drug delivery because of their nanoscale periodicity, permanent porosity, channel functionalization, and structural diversity. Despite these promising properties, the inherent structural features of even some of the best-performing MOFs make them moisture-sensitive and unstable in aqueous media, limiting their practical usefulness. This problem could be ...

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Section: Introductionmentioning

confidence: 99%

Hydrophobic Metal–Organic Frameworks

et al. 2019

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“…Fluorinated MOFs are of great interest because of their improved properties compared with their nonfluorinated counterparts. The increased hydrophobicity raises the performance in gas separation ( Mondal et al, 2017 ; Cheplakova et al, 2018 ), gas storage ( Zhang et al, 2013 ), or in the cleanup of oil spillages ( Yang et al, 2011 ). Metal-free carbon materials with heteroatom-doping (F, N) show electrocatalytic ORR activity ( Lv et al, 2017 ).…”

Section: Resultsmentioning

confidence: 99%

Mechanochemical Synthesis of Fluorine-Containing Co-Doped Zeolitic Imidazolate Frameworks for Producing Electrocatalysts

et al. 2022

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Catalysts derived from pyrolysis of metal organic frameworks (MOFs) are promising candidates to replace expensive and scarce platinum-based electrocatalysts commonly used in polymer electrolyte membrane fuel cells. MOFs contain ordered connections between metal centers and organic ligands. They can be pyrolyzed into metal- and nitrogen-doped carbons, which show electrocatalytic activity toward the oxygen reduction reaction (ORR). Furthermore, metal-free heteroatom-doped carbons, such as N-F-Cs, are known for being active as well. Thus, a carbon material with Co-N-F doping could possibly be even more promising as ORR electrocatalyst. Herein, we report the mechanochemical synthesis of two polymorphs of a zeolitic imidazole framework, Co-doped zinc 2-trifluoromethyl-1H-imidazolate (Zn0.9Co0.1(CF3-Im)2). Time-resolved in situ X-ray diffraction studies of the mechanochemical formation revealed a direct conversion of starting materials to the products. Both polymorphs of Zn0.9Co0.1(CF3-Im)2 were pyrolyzed, yielding Co-N-F containing carbons, which are active toward electrochemical ORR.

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“…The best performance is shown by Fe-PF2 which, to date, outperforms most of MOFs with fluorinated ligands, except for TKL-107. [42][43][44][45][46][47][48] Under the mild conditions of 298 K and 1 bar, it adsorbs 3.2 mmol/g (14% by weight), thus outperforming several MOFs including SNU-50, MOF-505, MOF-5, PCN-61, UiO-66 and IRMOF-74 functionalized with alkylamino groups. 16,49 N2 adsorption isotherms from 273 K to 298 K show a much lower adsorption capacity than those for CO2, suggesting an efficient selectivity in favour of CO2, as calculated by Ideal Adsorbed Solution Theory (IAST) (Fig.…”

Section: Gas Adsorptionmentioning

confidence: 99%

Reorientable fluorinated aryl rings in triangular channel Fe-MOFs: an investigation on CO₂–matrix interactions

et al. 2020

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Metal–organic frameworks based on octafluorobiphenyl-4,4′-dicarboxylate: synthesis, crystal structure, and surface functionality

Cited by 32 publications

References 43 publications

Hydrophobic Metal–Organic Frameworks

Hydrophobic Metal–Organic Frameworks

Mechanochemical Synthesis of Fluorine-Containing Co-Doped Zeolitic Imidazolate Frameworks for Producing Electrocatalysts

Reorientable fluorinated aryl rings in triangular channel Fe-MOFs: an investigation on CO₂–matrix interactions

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Metal–organic frameworks based on octafluorobiphenyl-4,4′-dicarboxylate: synthesis, crystal structure, and surface functionality

Cited by 32 publications

References 43 publications

Hydrophobic Metal–Organic Frameworks

Hydrophobic Metal–Organic Frameworks

Mechanochemical Synthesis of Fluorine-Containing Co-Doped Zeolitic Imidazolate Frameworks for Producing Electrocatalysts

Reorientable fluorinated aryl rings in triangular channel Fe-MOFs: an investigation on CO2–matrix interactions

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Reorientable fluorinated aryl rings in triangular channel Fe-MOFs: an investigation on CO₂–matrix interactions