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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5,461 citations
TL;DR: This review intends to provide an update of work published since then and focuses on the photoluminescence properties of MOFs and their possible utility in chemical and biological sensing and detection.
Abstract: Metal–organic frameworks (MOFs) are a unique class of crystalline solids comprised of metal cations (or metal clusters) and organic ligands that have shown promise for a wide variety of applications Over the past 15 years, research and development of these materials have become one of the most intensely and extensively pursued areas A very interesting and well-investigated topic is their optical emission properties and related applications Several reviews have provided a comprehensive overview covering many aspects of the subject up to 2011 This review intends to provide an update of work published since then and focuses on the photoluminescence (PL) properties of MOFs and their possible utility in chemical and biological sensing and detection The spectrum of this review includes the origin of luminescence in MOFs, the advantages of luminescent MOF (LMOF) based sensors, general strategies in designing sensory materials, and examples of various applications in sensing and detection
3,485 citations
TL;DR: This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovSKite family for electronic, optical, and energy-based applications as well as fundamental research.
Abstract: Although known since the late 19th century, organic–inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic–inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.
1,962 citations
TL;DR: In this paper, a general approach for the synthesis of hollow frameworks of nitrogen-doped carbon nanotubes derived from metal-organic frameworks, which exhibit higher electrocatalytic activity and stability for oxygen reduction and evolution than commercial Pt/C catalysts, is presented.
Abstract: Oxygen electrocatalysis is of great importance for many energy storage and conversion technologies, including fuel cells, metal–air batteries and water electrolysis. Replacing noble metal-based electrocatalysts with highly efficient and inexpensive non-noble metal-based oxygen electrocatalysts is critical for the practical applications of these technologies. Here we report a general approach for the synthesis of hollow frameworks of nitrogen-doped carbon nanotubes derived from metal–organic frameworks, which exhibit higher electrocatalytic activity and stability for oxygen reduction and evolution than commercial Pt/C electrocatalysts. The remarkable electrochemical properties are mainly attributed to the synergistic effect from chemical compositions and the robust hollow structure composed of interconnected crystalline nitrogen-doped carbon nanotubes. The presented strategy for controlled design and synthesis of metal–organic framework-derived functional nanomaterials offers prospects in developing highly active electrocatalysts in electrochemical energy devices. Precious metals are efficient oxygen electrocatalysts but suffer from poor stability and high cost. Now, nitrogen-doped carbon nanotubes derived from metal–organic frameworks are shown to have activity and durability comparable to that of Pt/C catalysts.
1,885 citations
1,800 citations
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TL;DR: Control experiments with dendritic aromatic aldehydes of different sizes indicate that the heterogeneous asymmetric catalyst derived from 1 is both highly active and enantioselective as a result of the creation of readily accessible, uniform active catalyst sites inside the porous MOF.
Abstract: A homochiral porous noninterpenetrating metal−organic framework (MOF), 1, was constructed by linking infinite 1D [Cd(μ-Cl)2]n zigzag chains with axially chiral bipyridine bridging ligands containing orthogonal secondary functional groups. The secondary chiral dihydroxy groups accessible via the large open channels in 1 were utilized to generate a heterogeneous asymmetric catalyst for the addition of diethyzinc to aromatic aldehydes to afford chiral secondary alcohols at up to 93% enantiomeric excess (ee). Control experiments with dendritic aromatic aldehydes of different sizes indicate that the heterogeneous asymmetric catalyst derived from 1 is both highly active and enantioselective as a result of the creation of readily accessible, uniform active catalyst sites inside the porous MOF.
1,720 citations
"The Chemistry and Applications of M..." refers background or methods in this paper
...[1,1′-binaphthalene]-2,2′-diol (DCDPBN), [CdCl2(DCDPBN)], used orthogonal dihydroxy functionalities to coordinate titanium isopropoxide [Ti(OPr)4], thus yielding a highly active, enantioselective asymmetric Lewis acid catalyst (67)....
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...olefin epoxidation and diethyl zinc (ZnEt2) additions to aromatic aldehydes, respectively (67, 77)....
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TL;DR: The results suggest that under low-loading conditions, the H(2) adsorption behavior of MOFs can be improved by imparting larger charge gradients on the metal oxide units and adjusting the link metrics to constrict the pore dimensions; however, a large pore volume is still a prerequisite feature.
Abstract: The dihydrogen adsorption isotherms of eight metal-organic frameworks (MOFs), measured at 77 K up to a pressure of 1 atm, have been examined for correlations with their structural features. All materials display approximately Type I isotherms with no hysteresis, and saturation was not reached for any of the materials under these conditions. Among the six isoreticular MOFs (IRMOFs) studied, the catenated materials exhibit the largest capacities on a molar basis, up to 9.8 H(2) per formula unit. The addition of functional groups (-Br, -NH(2), -C(2)H(4)-) to the phenylene links of IRMOF-1 (MOF-5), or their replacement with thieno[3,2-b]thiophene moieties in IRMOF-20, altered the adsorption behavior by a minor amount despite large variations in the pore volumes of the resulting materials. In contrast, replacement of the metal oxide units with those containing coordinatively unsaturated metal sites resulted in greater H(2) uptake. The enhanced affinities of these materials, MOF-74 and HKUST-1, were further demonstrated by calculation of the isosteric heats of adsorption, which were larger across much of the range of coverage examined, compared to those of representative IRMOFs. The results suggest that under low-loading conditions, the H(2) adsorption behavior of MOFs can be improved by imparting larger charge gradients on the metal oxide units and adjusting the link metrics to constrict the pore dimensions; however, a large pore volume is still a prerequisite feature.
1,670 citations
"The Chemistry and Applications of M..." refers background in this paper
...In general, the functionality of organic linkers has little influence on hydrogen adsorption (86), whereas increasing the pore volume and surface area of MOFsmarkedly enhances the gravimetric hydrogen uptake at 77 K and high pressure, as exemplified by the low-density materials: NU-100 and MOF-210 exhibit hydrogen adsorption as high as 7....
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TL;DR: A strategy to expand the pore aperture of metal-organic frameworks (MOFs) into a previously unattained size regime (>32 angstroms) is reported, as evidenced by their permanent porosity and high thermal stability (up to 300°C).
Abstract: We report a strategy to expand the pore aperture of metal-organic frameworks (MOFs) into a previously unattained size regime (>32 angstroms). Specifically, the systematic expansion of a well-known MOF structure, MOF-74, from its original link of one phenylene ring (I) to two, three, four, five, six, seven, nine, and eleven (II to XI, respectively), afforded an isoreticular series of MOF-74 structures (termed IRMOF-74-I to XI) with pore apertures ranging from 14 to 98 angstroms. All members of this series have noninterpenetrating structures and exhibit robust architectures, as evidenced by their permanent porosity and high thermal stability (up to 300°C). The pore apertures of an oligoethylene glycol–functionalized IRMOF-74-VII and IRMOF-74-IX are large enough for natural proteins to enter the pores.
1,637 citations
"The Chemistry and Applications of M..." refers background in this paper
...Pore aperture IRMOF-74-XI 98 Å (22) Number of organic linkers MTV-MOF-5 8 (7)...
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...More important, the large pore aperture is of benefit to the surface modification of the pores with various functionalities without sacrificing the porosity (22)....
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TL;DR: In this article, a review of the area encompassing modified PFSA membranes, alternative sulfonated polymer and their composite membranes, and acid−base complex membranes is presented. But the authors do not discuss the performance of the composite membranes.
Abstract: The state-of-the-art of polymer electrolyte membrane fuel cell (PEMFC) technology is based on perfluorosulfonic acid (PFSA) polymer membranes operating at a typical temperature of 80 °C. Some of the key issues and shortcomings of the PFSA-based PEMFC technology are briefly discussed. These include water management, CO poisoning, hydrogen, reformate and methanol as fuels, cooling, and heat recovery. As a means to solve these shortcomings, high-temperature polymer electrolyte membranes for operation above 100 °C are under active development. This treatise is devoted to a review of the area encompassing modified PFSA membranes, alternative sulfonated polymer and their composite membranes, and acid−base complex membranes. PFSA membranes have been modified by swelling with nonvolatile solvents and preparing composites with hydrophilic oxides and solid proton conductors. DMFC and H2/O2(air) cells based on modified PFSA membranes have been successfully operated at temperatures up to 120 °C under ambient pressure...
1,595 citations
"The Chemistry and Applications of M..." refers background in this paper
..., Nafion); however, these polymers have some drawbacks, such as operation temperature, humidity, and cost (109)....
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...If MOFs are to serve as proton conductors for practical applications, they must be able to function at relatively high operating temperatures (120° to 180°C) and in anhydrous conditions (109)....
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TL;DR: This study demonstrates that physisorptive materials can achieve affinities and capacities competitive with amine sorbents while greatly reducing the energy cost associated with regeneration.
Abstract: A series of four isostructural microporous coordination polymers (MCPs) differing in metal composition is demonstrated to exhibit exceptional uptake of CO2 at low pressures and ambient temperature. These conditions are particularly relevant for capture of flue gas from coal-fired power plants. A magnesium-based material is presented that is the highest surface area magnesium MCP yet reported and displays ultrahigh affinity based on heat of adsorption for CO2. This study demonstrates that physisorptive materials can achieve affinities and capacities competitive with amine sorbents while greatly reducing the energy cost associated with regeneration.
1,590 citations
"The Chemistry and Applications of M..." refers background in this paper
...with open metal sites were found to have desirable high initial Qst values of 62 kJ/mol and 47 kJ/mol for MIL-101(Cr) and Mg-MOF-74, respectively (96, 97), thereby offering enhanced...
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