The Chemistry and Applications of Metal-Organic Frameworks
30 Aug 2013-Science (American Association for the Advancement of Science)-Vol. 341, Iss: 6149, pp 1230444-1230444
TL;DR: Metal-organic frameworks are porous materials that have potential for applications such as gas storage and separation, as well as catalysis, and methods are being developed for making nanocrystals and supercrystals of MOFs for their incorporation into devices.
Abstract: Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.
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TL;DR: In this paper, a synthetic strategy to integrate discrete coordination cages into extended porous materials by decorating opposite charges on the singular cage, which offers multidirectional electrostatic forces among cages and leads to a porous supramolecular ionic solid.
4 citations
TL;DR: In this paper, a permethylated ligand with lower surface energy is used in the coordination process of two-dimensional coordination polymers (2D CPs) to prevent the formation of noticeable interlayer interactions.
Abstract: Although three-dimensional metal-organic frameworks (3D MOFs) currently enjoy great attention in the scientific world due to their utility to address challenges concerning energy, environment cleaning and not only, very recently two-dimensional version of these, rather considered two-dimensional coordination polymers (2D CPs), have become of interest from the perspective of their approach as ultra-thin layered 2D materials. Different from the emerging 2D materials that are generally inorganic in nature (graphene or 2D allotropes of various elements, MXenes, etc.), 2D CPs contain both inorganic and organic blocks, offering wider possibilities for structural diversification and area of applicability. However, in the crystallization process, 2D CP layers often stack on the basis of intermolecular interactions, leading to higher dimensional materials, which limit the manifestation of the size-effect properties. Their isolation individually or in multilayers with thickness/surface aspect ratio as small as possible is a challenge that seeks solutions through top-down or bottom-up approaches, each of them having certain limits. An original pathway consists in the use of a permethylated ligand with lower surface energy which, through its orientation in the coordination process to the metal ion, favors the anisotropic growth of the polymer and ensures the shielding of the formed nanosheet structure preventing the establishment of noticeable interlayer interactions. Such unique two-dimensional coordination polymers recently reported by the authors and some new data about them are reviewed here from the perspective of their structural particularities, properties, reactivity, functionality, and reusability/recyclability potential.
4 citations
01 Jan 2020
TL;DR: In this paper, the authors proposed porous silicon as the key material to develop high-energy storage electrodes, where the physical properties, e.g., pore diameter, porosity, and pore length can be controlled by etching parameter and the functionalized nanostructured surfaces of porous silicon, might be the key materials to develop the high energy storage electrodes.
Abstract: Energy storage has been of a topic of curiosity since long for a persistent human activity. Storing power from several intermittent sources has been a great interest of scientific community and grows as the renewable energy industry begins to generate a larger fraction of overall energy consumption. Several renewable sources of energy exist, e.g., wind energy, solar energy, bioenergy, etc., but the problem is to store this energy and again reuse it when needed. For that an electrode is required that has high-energy storage capacity. The electrode that has a very large surface area, long durability, and high conductivity is prerequisite. Electrochemically prepared porous silicon where the physical properties, e.g., pore diameter, porosity, and pore length can be controlled by etching parameter and the functionalized nanostructured surfaces of porous silicon, might be the key material to develop high-energy storage electrodes.
4 citations
13 Aug 2020
TL;DR: In this article, the authors developed QSPRs from experimental data and insights are provided on how to improve storage and deliverable CH4 storage capacity based on material properties such as density, pore volume, and largest cavity diameter.
Abstract: Quantitative structure–property relationships (QSPRs) can be applied to metal–organic frameworks (MOFs) to allow for reasonable estimates to be made of the CH4 storage performance. QSPRs are available for CH4 storage of MOFs, but these were obtained from Grand Canonical Monte Carlo (GCMC) simulations which have come under scrutiny and of which the accuracy has been questioned. Here, QSPRs were developed from experimental data and insights are provided on how to improve storage and deliverable CH4 storage capacity based on material properties. Physical properties of MOFs, such as density, pore volume, and largest cavity diameter (LCD), and their significance for CH4 storage capacity were assessed. One relationship that was found is that CH4 gravimetric storage capacity is directly proportional to Brunauer–Emmett–Teller (BET) surface area (r2 > 90%). The QSPRs demonstrated the effect of van der Waals forces involved in CH4 adsorption. An assessment was made of the accuracy of QSPRs made by GCMC as compared to QSPRs derived from experimental data. Guidelines are provided for optimal design of MOFs, including density and pore volume. With the recent achievement of the gravimetric 2012 DOE CH4 storage target, the QSPRs presented here may allow for the prediction of structural descriptors for CH4 storage capacity and delivery.
4 citations
TL;DR: In this article, the dithiophosphato complex was reacted with the bifunctional ligands 3,5-di-(4-pyridyl)-1,2,4-thiadiazole (L1) and 3, 5-di-, 3,pyrideyl]-1, 2,4,5,4thiamide (L2).
Abstract: Coordinatively unsaturated dithiophosphato complex [Cd((MeO)2PS2)2] (1) was reacted with the bifunctional ligands 3,5-di-(4-pyridyl)-1,2,4-thiadiazole (L1) and 3,5-di-(3-pyridyl)-1,2,4-thiadiazole ...
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References
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TL;DR: This work has shown that highly porous frameworks held together by strong metal–oxygen–carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.
Abstract: The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.
8,013 citations
"The Chemistry and Applications of M..." refers background in this paper
...These materials are constructed by joining metal-containing units [secondary building units (SBUs)] with organic linkers, using strong bonds (reticular synthesis) to create open crystalline frameworks with permanent porosity (1)....
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...MOF-1001 [Zn4O(BPP34C10DA)3; BPP34C10DA = 4,4′-(2,5,8,11,14,16,19,22,25,28decaoxa-1,15(1,4)-dibenzenacyclooctacosaphane1(2),1(5)-diylbis(ethyne-2,1-diyl))dibenzoate] uses periodic crown ether receptors attached to the architectural framework; this endows the pore with active domains capable of molecular recognition of highly disordered guests in a stereoelectronically controlled fashion (Fig....
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...works inwhich single atomswere linked by ditopic coordinating linkers (1)....
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TL;DR: A critical review of the emerging field of MOF-based catalysis is presented and examples of catalysis by homogeneous catalysts incorporated as framework struts or cavity modifiers are presented.
Abstract: A critical review of the emerging field of MOF-based catalysis is presented. Discussed are examples of: (a) opportunistic catalysis with metal nodes, (b) designed catalysis with framework nodes, (c) catalysis by homogeneous catalysts incorporated as framework struts, (d) catalysis by MOF-encapsulated molecular species, (e) catalysis by metal-free organic struts or cavity modifiers, and (f) catalysis by MOF-encapsulated clusters (66 references).
7,010 citations
"The Chemistry and Applications of M..." refers background in this paper
...MOFs can be used to support homogeneous catalysts, stabilize short-lived catalysts, perform size selectivity, and encapsulate catalysts within their pores (70)....
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TL;DR: Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups and can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl.
Abstract: A strategy based on reticulating metal ions and organic carboxylate links into extended networks has been advanced to a point that allowed the design of porous structures in which pore size and functionality could be varied systematically. Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups –Br, –NH2, –OC3H7, –OC5H11, –C2H4, and –C4H4 and that its pore size can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl. We synthesized an isoreticular series (one that has the same framework topology) of 16 highly crystalline materials whose open space represented up to 91.1% of the crystal volume, as well as homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. One member of this series exhibited a high capacity for methane storage (240 cubic centimeters at standard temperature and pressure per gram at 36 atmospheres and ambient temperature), and others the lowest densities (0.41 to 0.21 gram per cubic centimeter) for a crystalline material at room temperature.
6,922 citations
"The Chemistry and Applications of M..." refers background in this paper
...changing its underlying topology) in the design of MOFs with ultrahigh porosity and unusually large pore openings (5)....
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...One of the smallest isoreticular structures of MOF-5 is Zn4O(fumarate)3 (34); one of the largest is IRMOF-16 [Zn4O(TPDC)3; TPDC 2– = terphenyl-4,4′′-dicarboxylate] (5) (fig....
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TL;DR: In this article, an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxyates.
Abstract: Open metal–organic frameworks are widely regarded as promising materials for applications1,2,3,4,5,6,7,8,9,10,11,12,13,14,15 in catalysis, separation, gas storage and molecular recognition. Compared to conventionally used microporous inorganic materials such as zeolites, these organic structures have the potential for more flexible rational design, through control of the architecture and functionalization of the pores. So far, the inability of these open frameworks to support permanent porosity and to avoid collapsing in the absence of guest molecules, such as solvents, has hindered further progress in the field14,15. Here we report the synthesis of a metal–organic framework which remains crystalline, as evidenced by X-ray single-crystal analyses, and stable when fully desolvated and when heated up to 300?°C. This synthesis is achieved by borrowing ideas from metal carboxylate cluster chemistry, where an organic dicarboxylate linker is used in a reaction that gives supertetrahedron clusters when capped with monocarboxylates. The rigid and divergent character of the added linker allows the articulation of the clusters into a three-dimensional framework resulting in a structure with higher apparent surface area and pore volume than most porous crystalline zeolites. This simple and potentially universal design strategy is currently being pursued in the synthesis of new phases and composites, and for gas-storage applications.
6,778 citations
"The Chemistry and Applications of M..." refers background in this paper
...A major advance in the chemistry of MOFs came in 1999 when the synthesis, x-ray singlecrystal structure determination, and low-temperature, low-pressure gas sorption properties were reported for the first robust and highly porousMOF,MOF-5 (13)....
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