Thermodynamics of adsorption of aromatic compounds from non-aqueous solutions by MIL-53(Al) metal-organic framework

Saifutdinov, B. R.; Konnov, M. E.; Исаева, В. И.; In, Mitskevich; Kustov, L. М.

doi:10.1007/s11172-017-1693-z

Cited by 9 publications

(5 citation statements)

References 20 publications

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“…The enthalpy of benzene adsorption from n-hexane on the HKUST-1solv.1 sample is ∆H • = +28.35 kJ/mol, the adsorption entropy is ∆S • = +102.92 J/(mol K). Probably, the mechanism of the benzene liquid-phase adsorption on the HKUST-1solv.1 sample is similar to the entropy-driven mechanism of the liquid-phase adsorption of aromatics into the micropores of the MIL-53(Al) metal-organic framework [59]. Obviously, it means that benzene molecules with a critical diameter of 0.66 nm can penetrate into micropores of the HKUST-1solv.1 material.…”

Section: Study Of the Mechanism Of Liquid-phase Adsorption Onto Hkustmentioning

confidence: 77%

Section: Selectivity Of Aromatic Molecules Liquid-phase Adsorption Onmentioning

confidence: 99%

“…This adsorptive deformation involves tuning the pore geometry for the shape and size of the adsorbate molecules. Therefore, steric obstacles are a significant factor excluding the penetration of bulky adsorbate molecules in the HKUST-1 micropores, despite a larger pore size, than in the case of the MIL-53(Al) framework [20,59]. In order to evaluate the mechanical robustness of the material HKUST-1mw and the possibility of its shaping and compacting needed for some practical applications, its textural properties upon pressing were probed.…”

Section: Selectivity Of Aromatic Molecules Liquid-phase Adsorption Onmentioning

confidence: 99%

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Impact of the Preparation Procedure on the Performance of the Microporous HKUST-1 Metal-Organic Framework in the Liquid-Phase Separation of Aromatic Compounds

et al. 2020

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To date, metal-organic frameworks (MOFs) have been recognized as promising solid phases in high-performance liquid chromatography (HPLC). This research aimed to elucidate the role of the physico-chemical characteristics of the microporous HKUST-1 metal-organic framework in its operation as a selective adsorbent in HPLC. For this, the HKUST-1 samples were prepared by microwave-assisted synthesis and a solvothermal procedure. According to the chromatographic examinations, the HKUST-1 material synthesized in the microwave fields shows an efficient performance in the selective adsorption of aromatic compounds with different functionalities. This study revealed a significant impact of the preparation procedure on the mechanism of the liquid-phase adsorption on the HKUST adsorbents under conditions of the HPLC. An effect of the elution solvent with the different coordination ability to the Cu2+ sites in the HKUST-1 structure on the adsorption selectivity was observed.

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Section: Study Of the Mechanism Of Liquid-phase Adsorption Onto Hkustmentioning

confidence: 77%

Section: Selectivity Of Aromatic Molecules Liquid-phase Adsorption Onmentioning

confidence: 99%

Section: Selectivity Of Aromatic Molecules Liquid-phase Adsorption Onmentioning

confidence: 99%

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Impact of the Preparation Procedure on the Performance of the Microporous HKUST-1 Metal-Organic Framework in the Liquid-Phase Separation of Aromatic Compounds

et al. 2020

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“…Upon subsequent increasing the isopropanol volume fraction in the mobile phase, the Gibbs energy initially decreases in absolute value because of possible blockage of open metal Cu 2+ adsorption sites in HKUST-1 micropores by isopropanol molecules. Then the energy of adsorption slowly increases in an untrivial way due to a manifestation of peculiar mechanism of liquid-phase adsorption on microporous MOF that previously has been discovered for MIL-53(Al) framework [ 91 ]. In this area, there is even an entropy-driven mechanism of liquid-phase adsorption at the higher isopropanol volume fractions in the eluent ( Figure 12 ).…”

Section: Resultsmentioning

confidence: 99%

Understanding the Working Mechanism of the Novel HKUST-1@BPS Composite Materials as Stationary Phases for Liquid Chromatography

et al. 2022

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Composite materials have been used based on coordination polymers or microporous metal-organic frameworks (MOFs) combined with mesoporous matrices for adsorption-related techniques, which enable outflanking some adverse phenomena manifested during pristine components operation and enhance the performance and selectivity of the resulting materials. In this work, for the first time, the novel HKUST-1@BPS composites synthesized by the microwave-assisted (MW) technique starting from microporous HKUST-1 (Cu3(btc)2) MOF and biporous silica matrix (BPS) with bimodal mesopore size distribution were comparatively studied as materials for liquid-phase adsorption techniques utilizing the high-performance liquid chromatography (HPLC) method and benzene as a model adsorbate. It was established that the studied HKUST-1@BPS composites can function as stationary phases for HPLC, unlike the pristine HKUST-1 and bare BPS materials, due to the synergetic effect of both components based on the preliminary enhanced adsorbate mass transfer throughout the silica mesopores and, subsequently, its penetrating into HKUST-1 micropores. The suggested mechanism involves the initial deactivation of open metal Cu2+ sites in the HKUST-1 framework structure by isopropanol molecules upon adding this polar component into the mobile phase in the region of the isopropanol concentration of 0.0 to 0.2 vol.%. Thereafter, at the medium range of varying the isopropanol concentration in the eluent of 0.2 to 0.3 vol.%, there is an expansion of the previously inaccessible adsorption centers in the HKUST-1@BPS composites. Subsequently, while further increasing the isopropanol volume fraction in the eluent in the region of 0.3 to 5.0 vol.%, the observed behavior of the studied chromatographic systems is similar to the quasi-normal-phase HPLC pattern. According to the obtained thermodynamic data, benzene adsorption into HKUST-1 micropores from solutions with a vol.% of isopropanol in the range of 0.4 to 5.0 follows the unique entropy-driven mechanism previously described for the MIL-53(Al) framework. It was found that HKUST-1 loading in the composites and their preparation conditions have pronounced effects on their physicochemical properties and adsorption performance, including the adsorption mechanism.

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“…MIL-100(Fe) was used as the stationary phase for liquid chromatography (LC) to distinguish slight differences in adsorption behavior between the molecules. LC is a powerful tool not only for studying the adsorption behavior of many molecules, 14,22–24 but also for evaluating molecular adsorption on the stationary phase 25–28 because adsorption and desorption are repeated between the stationary and mobile phases in a separation column. To characterize the retention of the molecules, the retention factors ( k ) obtained from the LC measurements were compared with the log P OW values.…”

Section: Introductionmentioning

confidence: 99%

Cooperativity between coordinative unsaturated Fe(iii) and aryl-π electrons in MIL-100(Fe) for adsorption of small molecules

Tasaki-Handa,

Shibuya,

Saito

2024

New J. Chem.

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Thermodynamics of adsorption of aromatic compounds from non-aqueous solutions by MIL-53(Al) metal-organic framework

Cited by 9 publications

References 20 publications

Impact of the Preparation Procedure on the Performance of the Microporous HKUST-1 Metal-Organic Framework in the Liquid-Phase Separation of Aromatic Compounds

Impact of the Preparation Procedure on the Performance of the Microporous HKUST-1 Metal-Organic Framework in the Liquid-Phase Separation of Aromatic Compounds

Understanding the Working Mechanism of the Novel HKUST-1@BPS Composite Materials as Stationary Phases for Liquid Chromatography

Cooperativity between coordinative unsaturated Fe(iii) and aryl-π electrons in MIL-100(Fe) for adsorption of small molecules

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