Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
05 Jul 2006-Proceedings of the National Academy of Sciences of the United States of America (National Academy of Sciences)-Vol. 103, Iss: 27, pp 10186-10191
TL;DR: Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity, high thermal stability, and remarkable chemical resistance to boiling alkaline water and organic solvents.
Abstract: Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(Al) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m 2 /g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.
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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.
10,934 citations
Cites background from "Exceptional chemical and thermal st..."
...The first example of aMOFwith exceptional chemical stability is zeolitic imidazolate framework–8 [ZIF8, Zn(MIm)2;MIm =2-methylimidazolate],which was reported in 2006 (56)....
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5,393 citations
TL;DR: Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, Jeffrey R. Long
Abstract: Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm, Tae-Hyun Bae, Jeffrey R. Long
5,389 citations
TL;DR: The Zr-MOFs presented in this work have the toughness needed for industrial applications; decomposition temperature above 500 degrees C and resistance to most chemicals, and they remain crystalline even after exposure to 10 tons/cm2 of external pressure.
Abstract: Porous crystals are strategic materials with industrial applications within petrochemistry, catalysis, gas storage, and selective separation Their unique properties are based on the molecular-scale porous character However, a principal limitation of zeolites and similar oxide-based materials is the relatively small size of the pores, typically in the range of medium-sized molecules, limiting their use in pharmaceutical and fine chemical applications Metal organic frameworks (MOFs) provided a breakthrough in this respect New MOFs appear at a high and an increasing pace, but the appearances of new, stable inorganic building bricks are rare Here we present a new zirconium-based inorganic building brick that allows the synthesis of very high surface area MOFs with unprecedented stability The high stability is based on the combination of strong Zr−O bonds and the ability of the inner Zr6-cluster to rearrange reversibly upon removal or addition of μ3-OH groups, without any changes in the connecting carbox
4,958 citations
TL;DR: This critical review of the current status of hydrogen storage within microporous metal-organic frameworks provides an overview of the relationships between structural features and the enthalpy of hydrogen adsorption, spectroscopic methods for probing framework-H(2) interactions, and strategies for improving storage capacity.
Abstract: New materials capable of storing hydrogen at high gravimetric and volumetric densities are required if hydrogen is to be widely employed as a clean alternative to hydrocarbon fuels in cars and other mobile applications. With exceptionally high surface areas and chemically-tunable structures, microporous metal–organic frameworks have recently emerged as some of the most promising candidate materials. In this critical review we provide an overview of the current status of hydrogen storage within such compounds. Particular emphasis is given to the relationships between structural features and the enthalpy of hydrogen adsorption, spectroscopic methods for probing framework–H2 interactions, and strategies for improving storage capacity (188 references).
4,511 citations
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
TL;DR: In this paper, a family of highly ordered mesoporous (20−300 A) structures have been synthesized by the use of commercially available nonionic alkyl poly(ethylene oxide) (PEO) oligomeric surfactants and poly(alkylene oxide) block copolymers in acid media.
Abstract: A family of highly ordered mesoporous (20−300 A) silica structures have been synthesized by the use of commercially available nonionic alkyl poly(ethylene oxide) (PEO) oligomeric surfactants and poly(alkylene oxide) block copolymers in acid media. Periodic arrangements of mescoscopically ordered pores with cubic Im3m, cubic Pm3m (or others), 3-d hexagonal (P63/mmc), 2-d hexagonal (p6mm), and lamellar (Lα) symmetries have been prepared. Under acidic conditions at room temperature, the nonionic oligomeric surfactants frequently form cubic or 3-d hexagonal mesoporous silica structures, while the nonionic triblock copolymers tend to form hexagonal (p6mm) mesoporous silica structures. A cubic mesoporous silica structure (SBA-11) with Pm3m diffraction symmetry has been synthesized in the presence of C16H33(OCH2CH2)10OH (C16EO10) surfactant species, while a 3-d hexagonal (P63/mmc) mesoporous silica structure (SBA-12) results when C18EO10 is used. Surfactants with short EO segments tend to form lamellar mesost...
6,274 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
Book•
12 Sep 2007
TL;DR: F framework type data sheets (arranged by 3-letter code in alphabetical order) and isotypic material index.
Abstract: Section Headings Preface Introduction and explanatory notes Framework type data sheets (arranged by 3-letter code in alphabetical order) Appendices Isotypic material index
2,384 citations