Comparative Study of Hydrogen Sulfide Adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) Metal−Organic Frameworks at Room Temperature

Hamon, Lomig; Serre, Christian; Devic, Thomas; Loiseau, Thierry; Millange, Franck; Férey, Gérard; Weireld, Guy De

doi:10.1021/ja901587t

Cited by 481 publications

(301 citation statements)

References 40 publications

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“…[1][2][3][4][5] As one of topical MOFs, porous chromium terephthalate with giant pores labeled MIL-101(Cr) possesses several unique features such as hierarchical pore structure 6 including a mesoporous zeotype architecture, mesoporous cages and microporous windows, outstanding sorption properties, numerous unsaturated metal cation sites, and high hydrothermal and chemical stability. These properties have led to a number of application potential in catalysis, gas storage, drug delivery and adsorptive separation.…”

mentioning

confidence: 99%

Effect of Diamine in Amine-Functionalized MIL-101 for Knoevenagel Condensation

Kasinathan¹,

Shim²,

Hwang³

et al. 2011

Bulletin of the Korean Chemical Society

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Crystalline Metal-Organic Frameworks (MOFs) are currently an important kind of advanced functional materials due to their novel coordination structures, diverse topologies, and potential applications.1-5 As one of topical MOFs, porous chromium terephthalate with giant pores labeled MIL-101(Cr) possesses several unique features such as hierarchical pore structure 6 including a mesoporous zeotype architecture, mesoporous cages and microporous windows, outstanding sorption properties, numerous unsaturated metal cation sites, and high hydrothermal and chemical stability. These properties have led to a number of application potential in catalysis, gas storage, drug delivery and adsorptive separation.7-10 One important challenge has to realize is funtionalization via incorporation of binding site or reactive centers for catalysis. The functionalization methods of metal organic frameworks (MOFs) in a wide range of applications are two possible approaches including pre-and postmodification with functional groups. 7,9-15The functionalized pores of MOFs can be used as active sites in base-catalyzed reactions.13,16-19 It was already described on an electrophilic surface functionalization of coordinatively unsaturated metal sites (CUS) with chelating agents or electron-rich molecules. MIL-101(Cr) may thus be finely tuned for catalytic applications in precise conditions. It is known that MIL-101(Cr) possesses two coordinatively unsaturated metal sites (CUS) in a trimeric Cr(III) octahedral cluster (Scheme 1) with terminal water molecules which are removable from the framework under vacuum or in an inert gas flow at 423 K for 12 h. This CUS as Lewis acid sites in the structure was usable for the surface functionalization 7 (Figure 1).Here we further explore the preparation of the aminegrafted MIL-101 as a heterogeneous base catalyst according to a pK a value of the functional diamine group and their catalytic activities in Knoevenagel condensation of benzaldehyde and ethylcynoacetate. The diamine compounds used for the functionalization include ethane-1,2-diamine (ED), butane-1,4-diamine (BD), decane-1,10-diamine (DD) and benzene-1,4-diamine (PD).The XRD patterns of functionalized samples show decrease of intensity. These results provide that the diamines were filled the pores of MIL-101. However, the patterns still show the high-crystalline frameworks and porous structures after functionalization. (Supplementary Materials, Figure S1) The structural details of the pores such as BET surface area, pore volume and pore size are exhibited in Supplementary Materials ( Figure S2 and Table S1).

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confidence: 99%

Effect of Diamine in Amine-Functionalized MIL-101 for Knoevenagel Condensation

Kasinathan¹,

Shim²,

Hwang³

et al. 2011

Bulletin of the Korean Chemical Society

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“…It should be noted that this is in agreement with our previous findings on the hydrogen uptake in these systems that did not seem to be influenced on the high loading (low interaction strength) regime by PSM or defects as the kinetic diameter of H2 is 2.9 Å, and thus the opening of the supercluster will not effectively increase the number of H2 molecules contained within (Szilágyi et al, 2014). We would like to point out that the observed CH4 uptake for MIL-101(Cr) is lower than what was published previously (Hamon et al, 2009), this is also underpinned by a higher than 100% relative weight loss upon thermal treatment (Figure 3), which may be indicative of either metal vacancies or impurities whose decomposition results in the formation of volatile products. In the case of the pristine MIL-101 and PSM samples, it is likely to be a consequence of the latter one, which is also supported by the observed surface area being smaller than published elsewhere (Kim et al, 2013).…”

Section: Resultsmentioning

confidence: 50%

The Impact of Post-Synthetic Linker Functionalization of MOFs on Methane Storage: The Role of Defects

et al. 2016

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Natural gas is increasingly being viewed as one of the most viable alternatives to gasoline. However, its vehicular application will only be widespread if safe and high-capacity methane stores are developed. In this work, we report an over 33% increase in methane uptake on a post-synthetically modified metal-organic framework. The underlying mechanism for this dramatic increase is due to lattice defects formed upon post-synthetic modification. This method may open new approaches to natural gas storage.

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“…MOFs such as MIL-47 (V), MIL-53(Al, Cr) with saturated metal center show weak interaction with H 2 S and adsorption/desorption behavior is completely reversible in isotherm measurement. For some MOFs structures MIL-101(Cr), HKUST-1 with unsaturated metal sites [28,29], the adsorption of H 2 S is quite reactive, leading to release of BTC ligand from coordination with copper metal center and the formation of carboxlyate C═O group as indicated by the appearing of a band at 1710 cm . MOF-74 with nickel center shows a strong binding strength toward H 2 S with an adsorption heat ΔH ads of ~57 kJ/mol [30].…”

Section: Reactive Gas Moleculesmentioning

confidence: 99%

Interaction of Small Molecules within Metal Organic Frameworks Studied by In Situ Vibrational Spectroscopy

Tan¹,

Chabal²

2016

Metal-Organic Frameworks

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Molecular-level characterization of interaction between small gases and metal organic frameworks (MOFs) is crucial to elucidate the adsorption mechanism and establish the relationship between the structure and chemical features of MOFs with observed adsorptive properties, which ultimately guide the new structure design and synthesis for enhanced functional performance. Among different techniques, vibrational spectroscopy (infrared and Raman), which provides fingerprint of chemical bonds by their vibrational spectra, is one of the most powerful tools to study adsorbate-adsorbent interaction and give rich detailed information for molecular behaviors inside MOFs pores. This chapter reviews a number of exemplary works utilizing vibrational spectroscopy to study the interaction of small molecules with metal organic frameworks.

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Comparative Study of Hydrogen Sulfide Adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) Metal−Organic Frameworks at Room Temperature

Cited by 481 publications

References 40 publications

Effect of Diamine in Amine-Functionalized MIL-101 for Knoevenagel Condensation

Effect of Diamine in Amine-Functionalized MIL-101 for Knoevenagel Condensation

The Impact of Post-Synthetic Linker Functionalization of MOFs on Methane Storage: The Role of Defects

Interaction of Small Molecules within Metal Organic Frameworks Studied by In Situ Vibrational Spectroscopy

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