Synthesis and gas sorption properties of halogen-doped mesoporous chromium(iii) terephthalate

Berdonosova, Elena; Maletskaya, Nina V.; Kogan, E. V.; Kovalenko, Konstantin A.; Klyamkin, S. N.; Dybtsev, Danil N.; Fedin, Vladimir P.

doi:10.1007/s11172-013-0023-3

Cited by 8 publications

(9 citation statements)

References 28 publications

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“…The calculated parameters of porous structures are given in Table . Oxidizing compounds 1 and 2 into 3 and 4 correspondingly leads to a slightly decrease of the surface area and pore volume because of partial channel blocking by bromide, which is not surprising in the case of charged frameworks . The hypothesis is confirmed by a comparison of the pore-size distributions.…”

Section: Results and Discussionmentioning

confidence: 58%

Multifunctional Metal–Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters

et al. 2018

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The redox-active rhenium octahedral cluster unit [ReSe(CN)] was combined with Gd ions and dicarboxylate linkers in novel types of metal-organic frameworks (MOFs) that display a set of functional properties. The hydrolytically stable complexes [{Gd(HO)}(L)ReSe(CN)]·nHO (1, L = furan-2,5-dicarboxylate, fdc; 2, L = thiophene-2,5-dicarboxylate, tdc) exhibit a 3D framework of trigonal symmetry where 1D chains of [{Gd(HO)}(L)] are connected by [ReSe(CN)] clusters. Frameworks contain spacious channels filled with HO. Solvent molecules can be easily removed under vacuum to produce permanently porous solids with high volumetric CO uptake and remarkable CO/N selectivity at room temperature. The frameworks demonstrate an ability for reversible redox transformations of the cluster fragment. The orange powders of compounds 1 and 2 react with Br, yielding dark-green powders of [{Gd(HO)}(L)ReSe(CN)]Br·nHO (3, L = fdc; 4, L = tdc). Compounds 3 and 4 are isostructural with 1 and 2 and also have permanently porous frameworks but display different optical, magnetic, and sorption properties. In particular, oxidation of the cluster fragment "switches off" its luminescence in the red region, and the incorporation of Br leads to a decrease of the solvent-accessible volume in the channels of 3 and 4. Finally, the green powders of 3 and 4 can be reduced back to the orange powders of 1 and 2 by reaction with hydrazine, thus displaying a rare ability for fully reversible chemical redox transitions. Compounds 1-4 are mentioned as a new class of redox-active cluster-based MOFs with potential usage as multifunctional materials for gas separation and chemical contamination sensors.

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Section: Results and Discussionmentioning

confidence: 58%

Multifunctional Metal–Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters

et al. 2018

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“…The material was obtained by a published method. 19 Cr-MIL-101 (0.6 g, 0.5 mmol) was added to 5 mL of 1 M NaCl (5 mmol) solution. The mixture was stirred for 2 h at room temperature.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…20 A similar conclusion was reached in our previous work in which we demonstrated a 10% increase of methane adsorption capacity in spite of a two-fold smaller specific surface area after complete removal of fluoride by sodium chloride solution washing. 19 Along with postsynthetic modification methods aimed at elimination of fluorine ion from MIL-101, a direct synthesis route in absence of HF is available. The present work is devoted to a comparative study of porous structure and gas sorption (N 2 , H 2 , CH 4 ) features of Cr-MIL-101 with various amounts of fluorine anions.…”

Section: ■ Introductionmentioning

confidence: 99%

Influence of Anion Composition on Gas Sorption Features of Cr-MIL-101 Metal–Organic Framework

et al. 2015

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A series of chromium(III) terephthalates MIL-101 with different anion composition of the porous matrix have been synthesized and characterized in adsorption reactions with nitrogen, hydrogen, and methane by volumetric and calorimetric measurements at pressures up to 3.2 MPa. A peculiar local maximum of H2 adsorption heat at concentrations of 0.7–0.9 mmol/g corresponding to the filling of nanosized supertetrahedra was found. It has been shown that the substitution of the fluorine anions by Cl– strongly affected accessibility of these micropores toward gas molecules.

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“…Comparison of isotherms at ambient temperatures. (a) Adsorption isotherm at 298 K; (b) adsorption isotherm at 303 K; (c) total adsorption isotherm at 303 K; (d) adsorption isotherm at room temperature; (e) adsorption isotherm at 300 K; (f) excess adsorption isotherm at 303.1 K; (g) excess adsorption isotherm at 319 K; (h) excess adsorption isotherm at 300 K; (i) total adsorption isotherm at 297 K; (j) adsorption isotherm at 303.15 K; *not specified whether the isotherm is in terms of excess, absolute, or total adsorption; excess adsorption isotherms are marked by hollow interior; isotherm c is specified as absolute adsorption isotherm, but we marked it as total adsorption isotherm in consideration of their measuring method and the comparation with other literature reports.…”

Section: Results and Discussionmentioning

confidence: 99%

“…In MOFs, the arrangement of organic ligands and metal ions or clusters can form different intramolecular pore structures . The BET surfaces of MOFs range from 308 to 6240 m 2 g –1 , and the pore volumes range from 0.14 to 3.60 cm 3 g –1 . ,,− COF materials are entirely composed of light elements which are connected by covalent bonds. , COFs exhibit a low density, high stability, large BET specific surface of 750–3620 m 2 g –1 , and pore volume of 0.30–1.55 cm 3 g –1 . ,, Different from COFs, POPs are mostly noncrystalline. , The BET specific surface of POPs ranges from 1249 to 6461 m 2 g –1 , and the pore volume ranges from 0.45 to 3.04 cm 3 g –1 . ,− Due to the high specific surface and pore volume, MOFs, COFs, and POPs all exhibit a high gravimetric storage amount. Compared with MOFs, low density restricts the volumetric total methane uptake of COFs and POPs .…”

Section: Introductionmentioning

confidence: 99%

Enhanced Methane Delivery in MIL-101(Cr) by Means of Subambient Cooling

et al. 2021

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Adsorbed natural gas (ANG) technology is the use of highly porous materials to store natural gas at more reasonable pressures and temperatures compared with conventional liquefied or compressed natural gas storage. Many different porous materials have been considered for ANG; however, there is still lack of research on adsorption capabilities of these porous materials at subambient temperatures and their adsorption kinetics in order to explore alternative approaches to enhance methane delivery. Here, we present a study on the adsorption isotherms and kinetics of methane in MIL-101(Cr) over the temperature range from 263.15 to 453.15 K and the pressure range from 0.5 to 15.0 MPa. Based on the measured excess adsorption amount and the modified Sips model, the total adsorption amount and the corresponding isosteric heat of total adsorption were extracted. The study reveals that the delivery amount of methane charged at 263.15 K and discharged at 303.15 K can be enhanced by 38.3% as compared to that charged and discharged at the same temperature of 303.15 K. The rate of methane adsorption is found to be controlled by the diffusion process, and the methane diffusivity through MIL-101(Cr) is estimated by fitting the transient adsorption curves with the Crank model.

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Synthesis and gas sorption properties of halogen-doped mesoporous chromium(iii) terephthalate

Cited by 8 publications

References 28 publications

Multifunctional Metal–Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters

Multifunctional Metal–Organic Frameworks Based on Redox-Active Rhenium Octahedral Clusters

Influence of Anion Composition on Gas Sorption Features of Cr-MIL-101 Metal–Organic Framework

Enhanced Methane Delivery in MIL-101(Cr) by Means of Subambient Cooling

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