Science Watch® - Tracking Trends and Performance in Basic Research
January/February 2004


 Chemists Work Their IRMOFs To Collect Gases in Cubic Cavities by John Emsley
WHAT'S HOT IN CHEMISTRY
Rank      Paper Citations This Period (Jul-Aug 03) Rank Last Period (May-Jun 03)
1 A.L. Spek, "Single-crystal structure validation with the program PLATON," J. Appl. Cryst., 36: 7-13, February 2003. [Utrecht U., Netherlands] *636LK 44 1
2 M. Eddaoudi, et al., "Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage," Science, 295(5554): 469-72, 18 January 2002. [U. Michigan, Ann Arbor; Arizona St. U., Tempe] *512YG 17 3
3 R.C. Jin, et al., "Photoinduced conversion of silver nanospheres to nanoprisms," Science, 294(5548): 1901-3, 30 November 2001. [Northwestern U., Evanston, IL] 497PQ 15
4 Z.A. Peng, X. Peng, "Nearly monodisperse and shape-controlled CdSe nanocrystals via alternative route: Nucleation and growth," J. Amer. Chem. Soc., 124(13): 3343-53, 3 April 2002. [U. Arkansas, Fayetteville] *538BD 14
5 W.U. Huynh, J.J. Dittmer, A.P. Alivisatos, "Hybrid nanorod-polymer solar cells," Science, 295(5564): 2425-7, 29 March 2002. [U. Calif., Berkeley; Lawrence Berkeley Natl. Lab., CA] *536QD 13 4
6 W. Wernsdorfer, et al., "Exchange-biased quantum tunneling in a supramolecular dimer of single-molecule magnets," Nature, 416(6879): 406-9, 28 March 2002. [CNRS, Lab. Louis Neel, Grenoble, France; U. Florida, Gainesville; U. Calif., San Diego] *534UX 13
7 T. Ohzuku, Y. Makimura, "Layered lithium insertion material of LiNi1/2Mn1/2O2: A possible alternative to LiCoO2 for advanced lithium-ion batteries," Chem. Lett., (8):744-5, 5 August 2001. [Osaka U., Japan] *463YL 13
8 J.G. Huddleston, et al., "Characterization and comparison of hydrophillic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation," Green Chem., 3(4): 156-64, August 2001. [U. Alabama, Tuscaloosa] *467LJ 12
9 K.-B. Lee, et al., "Protein nanoarrays generated by dip-pen nanolithography, " Science, 295(5560): 1702-5, 1 March 2002. [Northwestern U., Evanston, IL; U. Chicago, IL] *527XH 12
10 S.L. McGovern, et al., "A common mechanism underlying promiscuous inhibitors from virtual and high-throughput screening," J. Med. Chem., 45(8): 1712-22, 11 April 2002. [Northwestern U., Chicago, IL; Howard Hughes Med. Inst., Brandeis U., Waltham, MA] *538ZH 10
 SOURCE: ISI's Hot Papers DatabaseRead  the full legend.

In 1999, a paper by Omar Yaghi of the University of Michigan, and Michael O’Keeffe of Arizona State University, was published in Nature (402: 276-9, 1999; see Science Watch, May/June 2001]. It described a class of open lattice compounds with cube-like voids capable of retaining large numbers of smaller molecules. Paper #2 now reports how one of these compounds can hold a remarkable 240 cc/g of methane, and Yaghi speculates that it might well find application as a way of storing this gas. The paper also reports a better method of preparing such compounds, with yields of around 90%.

The compounds in question, which Yaghi calls IRMOFs (short for "isoreticular metal organic frameworks"), have OZn4 as their basic construction unit, the oxygen being at the center of a tetrahedron of zinc atoms. The zinc atoms are then interconnected through a variety of organic compounds that consist of benzene rings with diametrically opposed carboxylic acid groups and these define the sides of a cubic lattice. Paper #2 shows 16 such compounds of which the one with a cyclobutyl ring fused to the benzene group, labelled IRMOF-6, was best at storing methane. Compounds were made by heating solutions of zinc nitrate dissolved in the solvent dimethylformamide with the dicarboxylic acid, at around 100° C, in a closed vessel for several hours. The structures of all of the compounds were determined by X-ray crystallography.

The IRMOF with the largest cavity had a chain of three benzene rings separating the two carboxylic acid groups, and this could in theory accommodate a sphere of diameter 29 Å. Indeed, so voluminous are the voids in this compound that it has the lowest density of any crystalline solid ever recorded: 0.21 g/cm3. Nor do IRMOFs rely on their voids being packed with molecules to support the framework; they retain their shape even when their pores are empty, and are robust enough to be heated to 400° C. Similar compounds have been made in the past but their molecular scaffolding crumpled once their supporting molecules were removed.

Not surprisingly, the IRMOFs are being actively tested and developed by chemical, petrol, and auto companies as a means of storing gases such as hydrogen and methane. The compound most investigated for paper #2 was IRMOF-6, whose ability to absorb various vapors was assessed. For two of these, carbon tetrachloride and methylene chloride, the weight of vapor absorbed even exceeds the weight of the compound itself, reaching 1.2 g/g, whereas for other vapors, such as methane, benzene, and cyclohexane, the limit is 0.8 g/g. Under atmospheric pressure, the methane storing capacity of IRMOF-6 is 155 ccs/g but this can be increased to a maximum of 240 ccs/g by increasing the pressure to 36 atmospheres. This is well below the pressure of methane in conventional methane cylinders (200 atmospheres).

It is the uniqueness of Yaghi’s compounds that is attracting attention, and he speculates that they are only the first examples of a series of microporous compounds: "We are systematically changing the metrics and chemical functionality in periodic, crystalline, networks without destroying the original structure topology, and this is what makes IRMOFs unique," Yaghi tells Science Watch.

Currently his group is working on materials with even larger pores, and he sees what they are doing as only the beginning: "We are laying the conceptual foundations for reticular chemistry, which, as exemplified by IRMOFs, represents an approach to logical synthesis that has led to materials with dramatically enhanced porosity and specific surface area. We are now beginning to see its applicability to linking together other building blocks such as proteins and other biomolecules."

Yaghi is currently concentrating on the fuel of the future, hydrogen gas, whose storage presents particular problems that IRMOFs might well solve. He has already reported high H2 uptake in some of his compounds (see N.L. Rosi, et al., Science, 300[5622]: 1127-9, 2003). Indeed, judging by the number of molecules that some have already shown they can enclose, it might well be that a single cavity of a future IRMOF could hold more than 50 molecules of H2 end

Dr. John Emsley is based at the Department of Chemistry,
Cambridge University, U.K.

Science Watch®, January/February 2004, Vol. 15, No. 1
Citing URL: http://www.sciencewatch.com/jan-feb2004/sw_jan-feb2004_page7.htm

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