Chemistry and Applications of Porous Metal–Organic Frameworks

Müller, Ulrich; Schubert, Markus M.; Yaghi, Omar M.

doi:10.1002/9783527610044.hetcat0013

Cited by 26 publications

(17 citation statements)

References 83 publications

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“…Metal–organic frameworks (MOFs) represent a class of materials prepared by self‐assembly of metallic ions and organic ligands (usually carboxylate, sulfonate, or phosphonate), which results in the formation of well‐defined networks with high porosity 1–4. Owing to the diversity of chemistry (several metals can be used) and the diversity of the network geometry that can be designed (several organic ligands can be used), MOFs materials find applications in various fields such as gas adsorption, gas separation, catalysis 5, 6. Most MOFs exhibit a microporous structure, nevertheless a class of MOFs with larger pores, called MIL (Material of Institut Lavoisier), was recently synthesized by Férey and coworkers 7, 8.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Ammonia Adsorption Properties of Mesoporous Metal–Organic Framework (MIL(Fe))–Graphite Oxide Composites: Exploring the Limits of Materials Fabrication

Petit

Bandosz

2011

Adv Funct Materials

323

204

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Composites of MIL‐100(Fe) and graphite oxide (GO) were prepared with various ratios of the two components and tested for ammonia removal in dynamic conditions. The initial and exhausted samples were characterized by X‐ray diffraction, nitrogen adsorption, thermal analysis, Fourier Transform infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy. The results indicate that the formation of well‐defined MIL‐100(Fe)/GO composites is not favored. This is linked to the specific geometry of MIL‐100(Fe). The attachment of the GO carbon layers to the spherical cages of MIL‐100(Fe) (via coordination between the oxygen groups of GO and the metallic sites of the metal–organic framework) prevents the proper formation of the MIL‐100(Fe) structure. Therefore, the composite with the highest GO content has a lower porosity and smaller ammonia adsorption capacity than those calculated for the physical mixture of MIL‐100(Fe) and GO. The main mechanism of ammonia retention is via Brönsted interactions between ammonia and the water molecules present in MIL‐100(Fe). Nevertheless, the presence of excess water in the system lowers the acidity of the MIL material, and consequently causes a decrease in the ammonia adsorption. The Lewis interactions between ammonia and the metal centers in MIL also take place during the adsorption process.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Ammonia Adsorption Properties of Mesoporous Metal–Organic Framework (MIL(Fe))–Graphite Oxide Composites: Exploring the Limits of Materials Fabrication

Petit

Bandosz

2011

Adv Funct Materials

323

204

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“…18 This feature makes these materials prime candidates for applications in gas purification, gas separation or heterogeneous catalysis. 19,20 Ammonia adsorption on MOF materials has been reported in a few studies. 7,21 Britt and coworkers have tested ammonia adsorption on six different MOFs: MOF-5, MOF-177, IRMOF-62, HKUST-1 (also called MOF-199), MOF-74 and IRMOF-3 with the best performances obtained with the last three materials.…”

Section: Introductionmentioning

confidence: 99%

Reactive Adsorption of Ammonia on Cu-Based MOF/Graphene Composites

2010

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New composites based on HKUST-1 and graphene layers are tested for ammonia adsorption at room temperature in both dry and moist conditions. The materials are characterized by Xray diffraction, FT-IR spectroscopy, adsorption of nitrogen and thermal analyses. Unlike other MOF/GO composites reported in previous studies, these materials are water stable. Ammonia adsorption capacities on the composites are higher than the ones calculated for the physical mixture of components, suggesting the presence of a synergetic effect between the MOF and graphene layers. The increased porosity and dispersive forces being the consequence of the presence of graphene layers are responsible for the enhanced adsorption. In addition to its retention via physical forces, ammonia is also adsorbed via binding to the copper sites in * To whom correpondance should be addressed. Telephone: 212-650-6017. Fax: 212-650-6107. E-mail: tbandosz@ccny.cuny.edu. 2HKUST-1 and then, progressively, via reaction with the MOF component. This reactive adsorption is visible through two successive changes of the adsorbents' color during the breakthrough tests. More ammonia is adsorbed in moist conditions than in dry conditions owing to its dissolution in a water film present in the pore system.

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“…Owing to their significant porosity and the small space they occupy, MOFs were tested in gas adsorption storage, separation, and purification. [30][31][32] For instance, tetrahydrothiophene adsorption has been studied on MOFs, and its performance competes with that of one of the common activated carbons. [31] In addition, a recent study on the adsorption of harmful gases (especially ammonia) using different types of MOFs has shown the importance of both the nature of the metal sites and the functionality of the organic linkers in the retention process.…”

Section: Introductionmentioning

confidence: 99%

“…In contrast, MOFs present a poor density of atoms and a completely open structure with enhanced diffusion coefficients. [32] Taking into account the complementary features of GO (welldeveloped chemistry with a rather dense arrangement of atoms) and MOFs (high porosity and versatility of functionality) in terms of adsorptive properties, we prepared MOF-5/GO nanocomposites and tested them for ammonia removal in dynamic conditions. GO was expected to favor dispersive forces and provide strong acidic groups able to react with ammonia while the MOF-5 component was expected to increase the porosity of the material and enable specific interactions of ammonia with the zinc species and the functional groups of the organic linker.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Adsorption of Ammonia on Metal‐Organic Framework/Graphite Oxide Composites: Analysis of Surface Interactions

Petit

Bandosz

2009

Adv Funct Materials

324

227

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Composites of the metal‐organic framework (MOF), MOF‐5, and graphite oxide (GO) with different ratios of the two components are prepared and tested in ammonia removal under dry conditions. The parent and composite materials are characterized before and after exposure to ammonia by sorption of N2, X‐ray diffraction, thermal analyses, and FT‐IR spectroscopy. The results show a synergetic effect resulting in an increase in the ammonia uptake compared to the parent materials. It is linked to enhanced dispersive forces in the pore space of the composites. Additionally, ammonia interacts with zinc oxide tetrahedra via hydrogen bonding and is intercalated between the layers of GO. Retention of a large quantity of ammonia eventually leads to a collapse of the MOF‐5 structure in the composites. The effect resembles that observed when MOF‐5 is exposed to water. Taking into account the similarity of ammonia and water molecules, it is hypothesized that ammonia causes a destruction of the MOF‐5 and composite structure as a result of its hydrogen bonding with the zinc oxide clusters.

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Chemistry and Applications of Porous Metal–Organic Frameworks

Abstract: The sections in this article are Introduction Terminology and Structure Synthesis Characterization Emerging Applications Adsorption Properties Diffusional Properties Gas Purification Gas Separation … Show more

Cited by 26 publications

References 83 publications

Synthesis, Characterization, and Ammonia Adsorption Properties of Mesoporous Metal–Organic Framework (MIL(Fe))–Graphite Oxide Composites: Exploring the Limits of Materials Fabrication

Synthesis, Characterization, and Ammonia Adsorption Properties of Mesoporous Metal–Organic Framework (MIL(Fe))–Graphite Oxide Composites: Exploring the Limits of Materials Fabrication

Reactive Adsorption of Ammonia on Cu-Based MOF/Graphene Composites

Enhanced Adsorption of Ammonia on Metal‐Organic Framework/Graphite Oxide Composites: Analysis of Surface Interactions

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