High uptakes of CO2 and CH4 in mesoporous metal-organic frameworks MIL-100 and MIL-101

Laboratoire Chimie Provence, Université de Provence - CNRS (UMR 6264), Centre de St Jérôme, 13397 Marseille Cedex 20, France.
Langmuir (Impact Factor: 4.46). 08/2008; 24(14):7245-50. DOI: 10.1021/la800227x
Source: PubMed


Mesoporous MOFs MIL-100 and MIL-101 adsorb huge amounts of CO2 and CH4. Characterization was performed using both manometry and gravimetry in different laboratories for isotherms coupled with microcalorimetry and FTIR to specify the gas-solid interactions. In particular, the uptake of carbon dioxide in MIL-101 has been shown to occur with a record capacity of 40 mmol g(-1) or 390 cm3STP cm(-3) at 5 MPa and 303 K.

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    • "Millward and Yaghi [20] studied the CO 2 adsorption on various MOFs and reported that the CO 2 uptake of MOF-177 was up to 33.5 mmol g À1 (35 bar, 298 K). MIL-101, one of the most stable MOFs containing ultra large cages, exhibited a CO 2 uptake up to 40 mmol g À1 (50 bar, 303 K) [21]. Babarao et al. [22] reported that the experimental adsorption capacity of IRMOF-1 (MOF-5) toward CO 2 was up to about 25 mmol g À1 (40 bar, 300 K). "
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    ABSTRACT: The composite GrO@MIL-101 has a higher surface area compared to its parent MIL-101. Its CO 2 capacity and selectivity were greatly enhanced due to the introduction of GrO. Its CO 2 adsorption capacity was up to 22.4 mmol/g at 25 bar and 298 K. Its adsorption selectivity for CO 2 /CH 4 (10:90) was up to 32 at 298 K. Desorption efficiency of CO 2 on GrO@MIL-101 was higher than 95%. g r a p h i c a l a b s t r a c t Keywords: Graphene oxide (GrO) MIL-101 GrO@MIL-101 composite CO 2 /CH 4 separation Selectivity a b s t r a c t A novel GrO@MIL-101 composite consisting of graphene oxide (GrO) and MIL-101(Cr) was synthesized, characterized and tested for separation of CO 2 /CH 4 mixture. GrO@MIL-101 had higher BET surface area and better porosity than parent MIL-101. CO 2 and CH 4 isotherms were separately measured at different temperatures using a gravimetric method, and were fitted using the dual-site Langmuir–Freundlich (DSLF) model. The adsorption capacity of GrO@MIL-101 for CO 2 was significantly improved over MIL-101, reaching 22.4 mmol g À1 at 25 bar and 298 K, much higher than traditional adsorbents and most other MOFs. The isotherms and selectivities of CO 2 /CH 4 binary mixture were estimated using the ideal adsorbed solution theory (IAST). While calculated isotherms indicated CO 2 was more favorably adsorbed on GrO@MIL-101 than CH 4 , the adsorption selectivity of GrO@MIL-101 composite was dramatically enhanced over pristine MIL-101. At 1.5 bar, the selectivity of GrO@MIL-101 for CO 2 /CH 4 (10:90) mixture with a characteristic of natural gas was up to 32, which was more than three times of that of MIL-101. Isosteric heats of adsorption for CO 2 and CH 4 on GrO@MIL-101 were slightly above those on parent MIL-101. GrO@MIL-101 also displayed remarkable quasi-reversibility for CO 2 adsorption, showing more than 95% desorption efficiency over five cycles.
    Full-text · Article · Apr 2015 · The Chemical Engineering Journal
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    • "Material Institute Lavoisier (MIL)-101(Cr), first reported by Ferey et al. [33], with a hybrid supertetrahedral building unit constructed by terephthalate ligands and trimeric chromium octahedral clusters, has high surface area, two types of mesoporous cages (29 and 34 Å in diameter) [34], and excellent chemical, hydrothermal stability. These features, in addition to the potential for generation of unsaturated chromium(III) sites in the framework on activation, make MIL-101(Cr) particularly attractive for practical applications involving selective gas adsorption, separation and heterogeneous catalysis [34] [35] [36] [37] [38]. In analytical technology, it has been applied as a stationary phase of GC capillary column to successfully separate the xylene isomers and ethylbenzene [39] [40]. "
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    ABSTRACT: Metal-organic frameworks (MOFs) have received great attention as novel sorbents due to their fascinating structures and intriguing potential applications in various fields. In this work, a MIL-101(Cr)-coated solid-phase microextraction (SPME) fiber was fabricated by a simple direct coating method and applied to the determination of volatile compounds (BTEX, benzene, toluene, ethylbenzene, m-xylene and o-xylene) and semi-volatile compounds (PAHs, polycyclic aromatic hydrocarbons) from water samples. The extraction and desorption conditions of headspace SPME (HS-SPME) were optimized. Under the optimized conditions, the established methods exhibited excellent extraction performance. Good precision (<7.7%) and low detection limits (0.32-1.7ngL(-1) and 0.12-2.1ngL(-1) for BTEX and PAHs, respectively) were achieved. In addition, the MIL-101(Cr)-coated fiber possessed good thermal stability, and the fiber can be reused over 150 times. The fiber was successfully applied to the analysis of BTEX and PAHs in river water by coupling with gas chromatography-mass spectrometry (GC-MS). The analytes at low concentrations (1.7 and 10ngL(-1)) were detected, and the recoveries obtained with the spiked river water samples were in the range of 80.0-113% and 84.8-106% for BTEX and PAHs, respectively, which demonstrated the applicability of the self-made fiber. Copyright © 2014 Elsevier B.V. All rights reserved.
    Full-text · Article · Jan 2015 · Analytica Chimica Acta
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    • "Since the introduction of the first porous MOF, more than 20 years ago, over 2000 threedimensional MOF topologies have been described. The large surface areas and tunable pore sizes of MOF makes them well suited for a variety of applications including gas storage, molecular sieving, sensors, medical imaging, drug release or heterogeneous catalysis (Eddaoudi et al., 2002; Alaerts et al., 2007; Harbuzaru et al., 2008; Llewellyn et al., 2008; Taylor et al., 2008; Farrusseng et al., 2009a; Horcajada et al., 2010). MOF are attractive materials since their structures can be designed at the atomic scale by an appropriate choice of metal and organic ligand. "
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    ABSTRACT: Two cobalt imidazolate metal–organic frameworks were evaluated as a bactericidal material against the growt h of the Gram-negative bacteria Pseudomonas putida and Escherichia coli. Under the most unfavourable conditions, within the exponential growth phase and in the culture media for both microorganisms, the growth inhibition reached over 50% for concentrations of biocidal material in the 5–10 mg L�-1 range. The release of metal gives excellent durability with the antibacterial effect persisting after 3 months. Both cobalt-based materials can be prepared with simple, cheap and easily accessible commercial ligands, leading to a more affordable possible future application as antimicrobial materials.
    Full-text · Article · Jun 2014 · Chemosphere
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