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: 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.
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1,800 citations
References
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3,087 citations
TL;DR: The design, synthesis and properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2 are reported, a new metal-organic framework with a surface area estimated at 4,500 m2 g-1 that combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules.
Abstract: One of the outstanding challenges in the field of porous materials is the design and synthesis of chemical structures with exceptionally high surface areas Such materials are of critical importance to many applications involving catalysis, separation and gas storage The claim for the highest surface area of a disordered structure is for carbon, at 2,030 m2 g(-1) (ref 2) Until recently, the largest surface area of an ordered structure was that of zeolite Y, recorded at 904 m2 g(-1) (ref 3) But with the introduction of metal-organic framework materials, this has been exceeded, with values up to 3,000 m2 g(-1) (refs 4-7) Despite this, no method of determining the upper limit in surface area for a material has yet been found Here we present a general strategy that has allowed us to realize a structure having by far the highest surface area reported to date We report the design, synthesis and properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2, a new metal-organic framework with a surface area estimated at 4,500 m2 g(-1) This framework, which we name MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules--attributes not previously combined in one material
2,540 citations
"The Chemistry and Applications of M..." refers background in this paper
...3A and 4) (15), which satisfies the above requirements....
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...The most effective way to prevent interpenetration is by making MOFs whose topology inhibits interpenetration because it would require the second framework to have a different topology (15)....
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TL;DR: A carbon dioxide storage system includes a container and a conduit attached to the container for introducing or removing a carbon dioxide-containing composition from the container as mentioned in this paper, which is positioned within the container.
Abstract: A carbon dioxide storage system includes a container and a conduit attached to the container for introducing or removing a carbon dioxide-containing composition from the container. A carbon dioxide storage material is positioned within the container. The carbon dioxide-storage material includes a metal-organic framework, which has a sufficient surface area to store at least 10 carbon dioxide molecules per formula unit of the metal-organic framework at a temperature of about 25° C.
2,320 citations
2,188 citations
"The Chemistry and Applications of M..." refers background in this paper
...The first example of catalysis in an extended framework, reported in 1994, involved the cyanosilylation of aldehydes in a Cd-based framework [Cd(BPy)2(NO3)2; BPy = 4,4′-bipyridine] as a result of axial ligand removal (29)....
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...2 cm (2)/V·s (27) Lithium storage capacity (after 60 cycles) Zn3(HCOO)6 560 mAh/g (28) Earliest report Catalysis by a MOF Cd(BPy)2(NO3)2 1994 (29)...
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TL;DR: The inclusion properties of the most open members are presented as evidence that MOF structures with rod building blocks can indeed be designed to have permanent porosity and rigid architectures.
Abstract: The principal structure possibilities for packing infinite rod-shaped building blocks are described. Some basic nets derived from linking simple rods (helices and ladders) are then enumerated. We demonstrate the usefulness of the concept of rod secondary building units in the design and synthesis of metal-organic frameworks (MOFs). Accordingly, we present the preparation, characterization, and crystal structures of 14 new MOFs (named MOF-69A-C and MOF-70-80) of 12 different structure types, belonging to rod packing motifs, and show how their structures are related to basic nets. The MOFs reported herein are of polytopic carboxylates and contain one of Zn, Pb, Co, Cd, Mn, or Tb. The inclusion properties of the most open members are presented as evidence that MOF structures with rod building blocks can indeed be designed to have permanent porosity and rigid architectures.
2,147 citations
"The Chemistry and Applications of M..." refers methods in this paper
...discrete inorganic SBUs, the infinite inorganic rod-type SBUs were also used to synthesize isostructural MOF-74 [Zn2(DOT); DOT = dioxidoterephthalate] (54) using divalent metal ions such as Mg, Co, Ni, and Mn (fig....
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...This strategy was implemented by expanding the original phenylene unit ofMOF-74 [M2(DOT); M 2+ = Zn, Mg] structure (54) to 2, 3, 4, 5, 6, 7, 9, and 11 phenylene units [DH2PhDC toDH11PhDC, respectively; Fig....
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