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Journal ArticleDOI

Ordered porous materials for emerging applications

20 Jun 2002-Nature (Nature Publishing Group)-Vol. 417, Iss: 6891, pp 813-821
TL;DR: The past decade has seen significant advances in the ability to fabricate new porous solids with ordered structures from a wide range of different materials, which has resulted in materials with unusual properties and broadened their application range beyond the traditional use as catalysts and adsorbents.
Abstract: "Space—the final frontier." This preamble to a well-known television series captures the challenge encountered not only in space travel adventures, but also in the field of porous materials, which aims to control the size, shape and uniformity of the porous space and the atoms and molecules that define it. The past decade has seen significant advances in the ability to fabricate new porous solids with ordered structures from a wide range of different materials. This has resulted in materials with unusual properties and broadened their application range beyond the traditional use as catalysts and adsorbents. In fact, porous materials now seem set to contribute to developments in areas ranging from microelectronics to medical diagnosis.
Citations
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Journal ArticleDOI
12 Jun 2003-Nature
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

Journal ArticleDOI
TL;DR: This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorbents in rigid and flexible MOFs, and primary relationships between adsorptive properties and framework features are analyzed.
Abstract: Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal–organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).

7,186 citations

Journal ArticleDOI
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

Journal ArticleDOI
15 Feb 2008-Science
TL;DR: Members of a selection of zeolitic imidazolate frameworks have high thermal stability and chemical stability in refluxing organic and aqueous media, and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2.
Abstract: A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390°C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO 2 capture from CO 2 /CO mixtures and extraordinary capacity for storing CO 2 : 1 liter of ZIF-69 can hold ∼83 liters of CO 2 at 273 kelvin under ambient pressure.

3,227 citations

References
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Journal ArticleDOI
22 Oct 1992-Nature
TL;DR: In this paper, the synthesis of mesoporous inorganic solids from calcination of aluminosilicate gels in the presence of surfactants is described, in which the silicate material forms inorganic walls between ordered surfactant micelles.
Abstract: MICROPOROUS and mesoporous inorganic solids (with pore diameters of ≤20 A and ∼20–500 A respectively)1 have found great utility as catalysts and sorption media because of their large internal surface area. Typical microporous materials are the crystalline framework solids, such as zeolites2, but the largest pore dimensions found so far are ∼10–12 A for some metallophosphates3–5 and ∼14 A for the mineral cacoxenite6. Examples of mesoporous solids include silicas7 and modified layered materials8–11, but these are invariably amorphous or paracrystalline, with pores that are irregularly spaced and broadly distributed in size8,12. Pore size can be controlled by intercalation of layered silicates with a surfactant species9,13, but the final product retains, in part, the layered nature of the precursor material. Here we report the synthesis of mesoporous solids from the calcination of aluminosilicate gels in the presence of surfactants. The material14,15 possesses regular arrays of uniform channels, the dimensions of which can be tailored (in the range 16 A to 100 A or more) through the choice of surfactant, auxiliary chemicals and reaction conditions. We propose that the formation of these materials takes place by means of a liquid-crystal 'templating' mechanism, in which the silicate material forms inorganic walls between ordered surfactant micelles.

15,125 citations


"Ordered porous materials for emergi..." refers background or methods in this paper

  • ...Although the report on MCM-41 by Kresge et al.(4) stimulated recent work on ordered materials with uniform mesoporosity, evidence that such materials could be prepared precedes their publication(31,32)....

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  • ...) Moreover, Kresge et al.(4) identified the connection between the ordering observed in the mesoporous materials and the structure-directing aggregation properties of the surfactants used in their synthesis....

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  • ...The work by Kresge et al.(4) was thus not in the absence of earlier claims of having prepared materials with uniform mesoporosity....

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  • ...As might be expected, the degree of ordering can depend significantly on the method used to synthesize the mesoporous material, ranging from the high degree of ordering first reported by Kresge et al.(4) to an almost complete lack of ordering....

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  • ...In fact, materials of the type reported by Kresge et al.(4) may have already been made decades ago: in 1971, a material described as low-bulk density silica was obtained through hydrolysing and condensing tetraethylorthosilicate in the presence of cationic surfactants(33)....

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Journal ArticleDOI
18 Jan 2002-Science
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


"Ordered porous materials for emergi..." refers background in this paper

  • ...However, metal–organic frameworks (MOFs) that exhibit permanent porosity have now been prepare...

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Journal ArticleDOI
18 Nov 1999-Nature
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

Journal ArticleDOI
TL;DR: Corma et al. as mentioned in this paper used the Dupont Award on new materials (1995), and the Spanish National Award “Leonardo Torres Quevedo” on Technology Research (1996) on technology research (1996), to recognize the performance of zeolites as catalysts for oil refining and petrochemistry.
Abstract: It is possible to say that zeolites are the most widely used catalysts in industry They are crystalline microporous materials which have become extremely successful as catalysts for oil refining, petrochemistry, and organic synthesis in the production of fine and speciality chemicals, particularly when dealing with molecules having kinetic diameters below 10 A The reason for their success in catalysis is related to the following specific features of these materials:1 (1) They have very high surface area and adsorption capacity (2) The adsorption properties of the zeolites can be controlled, and they can be varied from hydrophobic to hydrophilic type materials (3) Active sites, such as acid sites for instance, can be generated in the framework and their strength and concentration can be tailored for a particular application (4) The sizes of their channels and cavities are in the range typical for many molecules of interest (5-12 A), and the strong electric fields2 existing in those micropores together with an electronic confinement of the guest molecules3 are responsible for a preactivation of the reactants (5) Their intricate channel structure allows the zeolites to present different types of shape selectivity, ie, product, reactant, and transition state, which can be used to direct a given catalytic reaction toward the desired product avoiding undesired side reactions (6) All of these properties of zeolites, which are of paramount importance in catalysis and make them attractive choices for the types of processes listed above, are ultimately dependent on the thermal and hydrothermal stability of these materials In the case of zeolites, they can be activated to produce very stable materials not just resistant to heat and steam but also to chemical attacks Avelino Corma Canos was born in Moncofar, Spain, in 1951 He studied chemistry at the Universidad de Valencia (1967−1973) and received his PhD at the Universidad Complutense de Madrid in 1976 He became director of the Instituto de Tecnologia Quimica (UPV-CSIC) at the Universidad Politecnica de Valencia in 1990 His current research field is zeolites as catalysts, covering aspects of synthesis, characterization and reactivity in acid−base and redox catalysis A Corma has written about 250 articles on these subjects in international journals, three books, and a number of reviews and book chapters He is a member of the Editorial Board of Zeolites, Catalysis Review Science and Engineering, Catalysis Letters, Applied Catalysis, Journal of Molecular Catalysis, Research Trends, CaTTech, and Journal of the Chemical Society, Chemical Communications A Corma is coauthor of 20 patents, five of them being for commercial applications He has been awarded with the Dupont Award on new materials (1995), and the Spanish National Award “Leonardo Torres Quevedo” on Technology Research (1996) 2373 Chem Rev 1997, 97, 2373−2419

5,290 citations


"Ordered porous materials for emergi..." refers background in this paper

  • ..., as are reviews on microporous and ordered mesoporous materials syntheses and their applications as catalyst...

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Journal ArticleDOI
27 Apr 2000-Nature
TL;DR: The synthesis of a homochiral metal–organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantiOSElective manner is reported.
Abstract: Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.

3,598 citations