Dataset Information

An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance.

ABSTRACT: Vapor-assisted dry-gel synthesis of the metal-organic framework-74 (MOF-74) structure, specifically Ni-MOF-74 produced from synthetic precursors using an organic-water hybrid solvent system, showed a very high yield (>90% with respect to 2,5-dihydroxyterepthalic acid) and enhanced performance. The Ni-MOF-74 obtained showed improved sorption characteristics towards CO2 and the refrigerant fluorocarbon dichlorodifluoromethane. Unlike conventional synthesis, which takes 72?hours using the tetrahydrofuran-water system, this kinetic study showed that Ni-MOF-74 forms within 12?hours under dry-gel conditions with similar performance characteristics, and exhibits its best performance characteristics even after 24?hours of heating. In the dry-gel conversion method, the physical separation of the solvent and precursor mixture allows for recycling of the solvent. We demonstrated efficient solvent recycling (up to three times) that resulted in significant cost benefits. The scaled-up manufacturing cost of Ni-MOF-74 synthesized via our dry-gel method is 45% of conventional synthesis cost. Thus, for bulk production of the MOFs, the proposed vapor-assisted, dry-gel method is efficient, simple, and inexpensive when compared to the conventional synthesis method.

SUBMITTER: Das AK

PROVIDER: S-EPMC4910056 | biostudies-literature | 2016 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance.

Das Atanu Kumar AK Vemuri Rama Sesha RS Kutnyakov Igor I McGrail B Peter BP Motkuri Radha Kishan RK

Scientific reports 20160616

Vapor-assisted dry-gel synthesis of the metal-organic framework-74 (MOF-74) structure, specifically Ni-MOF-74 produced from synthetic precursors using an organic-water hybrid solvent system, showed a very high yield (>90% with respect to 2,5-dihydroxyterepthalic acid) and enhanced performance. The Ni-MOF-74 obtained showed improved sorption characteristics towards CO2 and the refrigerant fluorocarbon dichlorodifluoromethane. Unlike conventional synthesis, which takes 72 hours using the tetrahydr ...[more]

PMID: 27306598

Similar Datasets

Project description:The stability of functional materials in water-containing environments is critical for their industrial applications. A wide variety of metal-organic frameworks (MOFs) synthesized in the past decade have strikingly different apparent stabilities in contact with liquid or gaseous H2O, ranging from rapid hydrolysis to persistence over days to months. Here, we show using newly determined thermochemical data obtained by high-temperature drop combustion calorimetry that these differences are thermodynamically driven rather than primarily kinetically controlled. The formation reaction of a MOF from metal oxide (MO) and a linker generally liberates water by the reaction MO + linker = MOF + H2O. Newly measured enthalpies of formation of Mg-MOF-74(s) + H2O(l) and Ni-MOF-74(s) + H2O(l) from their crystalline dense components, namely, the divalent MO (MgO or NiO) and 2,5-dihydroxyterephthalic acid, are 303.9 ± 17.2 kJ/mol of Mg for Mg-MOF-74 and 264.4 ± 19.4 kJ/mol of Ni for Ni-MOF-74. These strongly endothermic enthalpies of formation indicate that the reverse reaction, namely, the hydrolysis of these MOFs, is highly exothermic, strongly suggesting that this large thermodynamic driving force for hydrolysis is the reason why the MOF-74 family cannot be synthesized via hydrothermal routes and why these MOFs decompose on contact with moist air or water even at room temperature. In contrast, other MOFs studied previously, namely, zeolitic imidazolate frameworks (ZIF-zni, ZIF-1, ZIF-4, Zn(CF3Im)2, and ZIF-8), show enthalpies of formation in the range 20-40 kJ per mole of metal atom. These modest endothermic enthalpies of formation can be partially compensated by positive entropy terms arising from water release, and these materials do not react appreciably with H2O under ambient conditions. Thus, these differences in reactivity with water are thermodynamically controlled and energetics of formation, either measured or predicted, can be used to assess the extent of water sensitivity for different possible MOFs.

Dataset Information

An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance.

Publications

An Efficient Synthesis Strategy for Metal-Organic Frameworks: Dry-Gel Synthesis of MOF-74 Framework with High Yield and Improved Performance.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets