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.

The Chemistry and Applications of Metal-Organic Frameworks

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

From Microporous to Mesoporous Molecular-Sieve Materials and Their Use in Catalysis

Natural gas hydrates are solid, non-stoichiometric compounds of small gas molecules and water. They form when the constituents come into contact at low temperature and high pressure. The physical properties of these compounds, most notably that they are non-flowing crystalline solids that are denser than typical fluid hydrocarbons and that the gas molecules they contain are effectively compressed, give rise to numerous applications in the broad areas of energy and climate effects. In particular, they have an important bearing on flow assurance and safety issues in oil and gas pipelines, they offer a largely unexploited means of energy recovery and transportation, and they could play a significant role in past and future climate change.

Fundamental principles and applications of natural gas hydrates

Dihydrogen, methane, and carbon dioxide isotherm measurements were performed at 1−85 bar and 77−298 K on the evacuated forms of seven porous covalent organic frameworks (COFs). The uptake behavior and capacity of the COFs is best described by classifying them into three groups based on their structural dimensions and corresponding pore sizes. Group 1 consists of 2D structures with 1D small pores (9 A for each of COF-1 and COF-6), group 2 includes 2D structures with large 1D pores (27, 16, and 32 A for COF-5, COF-8, and COF-10, respectively), and group 3 is comprised of 3D structures with 3D medium-sized pores (12 A for each of COF-102 and COF-103). Group 3 COFs outperform group 1 and 2 COFs, and rival the best metal−organic frameworks and other porous materials in their uptake capacities. This is exemplified by the excess gas uptake of COF-102 at 35 bar (72 mg g−1 at 77 K for hydrogen, 187 mg g−1 at 298 K for methane, and 1180 mg g−1 at 298 K for carbon dioxide), which is similar to the performance of COF...

http://yaghi.berkeley.edu/pdfPublications/Furukawa09.pdf

Storage of Hydrogen, Methane, and Carbon Dioxide in Highly Porous Covalent Organic Frameworks for Clean Energy Applications

The Stability of Cyclodextrin Complexes in Solution.

The storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy. Previous strategies--where hydrogen has been bound chemically, adsorbed in materials with permanent void space or stored in hybrid materials that combine these elements--have problems arising from either technical considerations or materials cost. A recently reported clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures (approximately 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to approximately 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.

Tuning clathrate hydrates for hydrogen storage

Clathrate hydrates, ice-like host–guest systems containing guest molecules in cages of hydrogen-bonded water molecules exist in three well-characterized cubic forms, and a less well-characterized tetragonal form1,2 On the basis of 2H and l29Xe NMR measurements and X-ray and neutron powder diffraction results, we now report a new hexagonal hydrate structure requiring both large and small guest molecules to stabilize the structure This hydrate is expected to be isostructural with the hexagonal clathrasil dodecasil-lH (see ref 14 for clathrasil nomenclature) As for the cubic clathrate hydrates, the new hydrate structure may occur naturally

A new clathrate hydrate structure

Metal organic frameworks (MOFs) are particularly exciting materials that couple porosity, diversity and crystallinity. But although they have been investigated for a wide range of applications, MOF chemistry focuses almost exclusively on properties intrinsic to the empty frameworks; the use of guest molecules to control functions has been essentially unexamined. Here we report Na(3)(2,4,6-trihydroxy-1,3,5-benzenetrisulfonate) (named β-PCMOF2), a MOF that conducts protons in regular one-dimensional pores lined with sulfonate groups. Proton conduction in β-PCMOF2 was modulated by the controlled loading of 1H-1,2,4-triazole (Tz) guests within the pores and reached 5 × 10(-4) S cm(-1) at 150 °C in anhydrous H(2), as confirmed by electrical measurements in H(2) and D(2), and by solid-state NMR spectroscopy. To confirm its potential as a gas separator membrane, the partially loaded MOF (β-PCMOF2(Tz)(0.45)) was also incorporated into a H(2)/air membrane electrode assembly. The resulting membrane proved to be gas tight, and gave an open circuit voltage of 1.18 V at 100 °C.

Anhydrous proton conduction at 150 °C in a crystalline metal–organic framework

A {sup 129}Xe NMR technique was developed to assess the clathrate hydrate forming ability of new potential guest molecules and to determine the structure of the resulting hydrates. About 25 new guests, mainly hydrocarbons, were identified as stabilizing the recently reported hexagonal hydrate, structure H. Successful tests of a few guests with different functional groups show that structure H represents a large new family of hydrate structures. New structure II hydrate formers include the first examples of ester and nitrile guests. It is shown that guests with maximum dimension larger than {approximately} 7.1 {angstrom} require the presence of a help gas to give a stable structure II hydrate and that guests larger than 7.5 {angstrom}, together with a suitable help gas, promote structure H. In addition to correct size, the guest molecule is required to have the correct shape for efficient space filling of the structure H large cage.

Christopher I. Ratcliffe

Papers

Tuning clathrate hydrates for hydrogen storage

A new clathrate hydrate structure

Anhydrous proton conduction at 150 °C in a crystalline metal–organic framework

Xenon-129 NMR studies of clathrate hydrates: new guests for structure II and structure H

Laboratory analysis of a naturally occurring gas hydrate from sediment of the Gulf of Mexico