Metal organic microporous materials

Matsuda, R., Kitaura, R., Kitagawa, S., et al., Highly controlled acetylene accommodation in a metal-organic microporous material. Nature 2005, 436, 238-241. 

O. M. Yaghi, Crystalline metal-organic microporous materials, (Nalco Chemical Company, USA). 1997, 95-560224, 5648508... 

Even though crystalline microporous materials include those with pore size between 10 and 20 A (called extra-large pore materials), few of them have a pore size within this range. This limits the applications of microporous materials to small molecules. There has always been a desire to increase the pore size of a crystalline material to more than 10 A while maintaining adequate thermal or hydrothermal stability required for various applications. Recent advances in chalcogenide and metal-organic framework materials have shown much promise for the preparation of extra-large pore materials. 

Dybtsev, D.N. Chun, H. Yoon, S.H. Kim, D. Kim, K. Microporous manganese formate a simple metal-organic porous material with high framework stability and highly selective gas sorption properties. J. Am. Chem. Soc. 2004, 126 (1), 32-33. 

Although catalysis is potentially one of the most important applications of metal-organic porous materials, as was the case for microporous zeolites and mesoporous materials, only a handful of examples have been so far reported for MOFs [128-131]. For catalytic applications using metal-organic open-framework materials, apparently five types of catalyst systems or active sites have been utilized ... 

Park YK, Choi S, Kim H, Kim K, Won B-H, Choi K, et al. Vapor phase inclusion of ferrocene and its derivative in a microporous metal-organic porous material and its structural characterization by single crystal X-ray diffraction. Angew Chem Int Ed 2007 46 8230-3. 

J. L. C. Rowsell and O. M. Yaghi, Metal-organic frameworks a new class of porous materials, Microporous Mesoporous Mater., 73, 3-14 (2004). 

The past nearly six decades have seen a chronological progression in molecular sieve materials from the aluminosilicate zeolites to microporous silica polymorphs, microporous aluminophosphate-based polymorphs, metallosilicate and metaHo-phosphate compositions, octahedral-tetrahedral frameworks, mesoporous molecular sieves and most recently hybrid metal organic frameworks (MOFs). A brief discussion of the historical progression is reviewed here. For a more detailed description prior to 2001 the reader is referred to [1]. The robustness of the field is evident from the fact that publications and patents are steadily increasing each year. 

The hydrothermal method has been employed in recent years to synthesize a variety of solids that include aluminium phosphates (ALPOs) and other microporous transition-metal phosphates and transition-metal polychalcogenides (Davis Lobo, 1992 Haushalter Mundi, 1992 Liao Kanatzidis, 1990, 1992). Unlike zeolites, synthesis of ALPOs requires acidic or mildly basic conditions and no alkali metal cations. A typical synthetic mixture for making ALPO consists of alumina, H3PO4, water and an organic material such as a quaternary ammonium salt or an amine. The hydrothermal reaction occurs around 373-573 K. The use of fluoride ions, instead of hydroxide ions as mineralizer, allows synthesis of novel microporous materials under acidic conditions (Estermann et al, 1991 Ferey et ai, 1994). 

Zeolites and related aluminosilicates constitute a vital family of microporous materials with immense applications in catalysis, sorption and separation processes [1-3]. The discovery of aluminophosphates is an important landmark in the science of these materials [4], All these materials are, in general, synthesized under hydrothermal conditions by making use of template molecules [2]. The template molecules are usually organic amines and they are involved in the formation of these framework structures in more ways than one. While it is difficult to pinpoint the exact manner in which the amines participate or direct the formation of these inorganic structures, it is generally believed that their size and shape are crucial in determining the pore structure. In recent years, a variety of open-framework structures formed by divalent metal phosphates... 

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