MOF----咪唑类羧酸

DOI: 10.1126/science.1083440

, 1127 (2003);

300 Science , et al.Nathaniel L. Rosi Hydrogen Storage in Microporous Metal-Organic Frameworks

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Hauschka,and C.E.Bronnimann for insightful discus-sions,and lea for assistance with procurement of the human bone specimens.A.Bielecki and D.Rice obtained preliminary demonstration spectra of test specimens.Supported by NIH grants AR42258(Na-tional Institute of Arthritis,Musculoskeletal,and Skin Disorders)and RR03264(Division of Research Re-sources).Supporting Online Material

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Materials and Methods Figs.S1and S2

16September 2002;accepted 11April 2003

Hydrogen Storage in Microporous Metal-Organic Frameworks

Nathaniel L.Rosi,1Juergen Eckert,2,3Mohamed Eddaoudi,4David T.Vodak,1Jaheon Kim,1Michael O’Keeffe,5Omar M.Yaghi 1*

Metal-organic framework-5(MOF-5)of composition Zn 4O(BDC)3(BDC ϭ1,4-benzenedicarboxylate)with a cubic three-dimensional extended porous struc-ture adsorbed hydrogen up to 4.5weight percent (17.2hydrogen molecules per formula unit)at 78kelvin and 1.0weight percent at room temperature and pressure of 20bar.Inelastic neutron scattering spectroscopy of the rotational transitions of the adsorbed hydrogen molecules indicates the presence of two well-defined binding sites (termed I and II),which we associate with hydrogen binding to zinc and the BDC linker,respectively.Preliminary studies on topo-logically similar isoreticular metal-organic framework-6and -8(IRMOF-6and -8)having cyclobutylbenzene and naphthalene linkers,respectively,gave ap-proximately double and quadruple (2.0weight percent)the uptake found for MOF-5at room temperature and 10bar.The development of hydrogen-fueled vehi-cles and portable electronics will require new materials that can store large amounts of hydrogen at ambient temperature and rela-tively low pressures with small volume,low weight,and fast kinetics for recharging (1,2).

A design target for automobile fueling has been set by the U.S.Department of Energy at 6.5%hydrogen by weight.

Metal hydride systems have been intense-ly examined in this respect (3),but there are many problems associated with their use,in-

cluding cost,low specific uptake by weight,unfavorable kinetics requiring heating cycles,and susceptibility to contamination by impu-rities.Various carbon-based adsorbents (e.g.,porous carbon,intercalated graphite,and nanotubes)have also been studied and,while promising,have been beset by mixed results (4,5).For these materials,it has been diffi-cult both to systematically engineer their mo-lecular structure and to identify specific hy-drogen binding sites.Here we report very favorable hydrogen sorption properties ob-tained at 78K or ambient temperature under safe pressures (up to 20bar)with crystalline metal-organic frameworks (MOFs)(6)hav-ing cubic cavities of uniform size and internal

1

Department of Chemistry,University of Michigan,Ann Arbor,MI 48109,USA.2Materials Research Lab-oratory,University of California,Santa Barbara,CA 93106,USA.3Los Alamos Neutron Science Center,Los Alamos National Laboratory,Los Alamos,NM 87545,USA.4Department of Chemistry,University of South Florida,4202East Fowler Avenue,SCA 400,Tampa,FL 33620–5250,USA.5Department of Chemistry,Arizo-na State University,Tempe,AZ 85287,USA.

*To whom correspondence should be addressed.E-mail:

oyaghi@

Fig.1.Single-crystal x-ray structures of MOF-5(A ),IRMOF-6(B ),and IRMOF-8(C )illustrated for a single cube fragment of their respective cubic three-dimensional extended structure.On each of the corners is a cluster [OZn 4(CO 2)6]of an oxygen-centered Zn 4tetrahedron that is

bridged by six carboxylates of an organic linker (Zn,blue polyhedron;O,red spheres;C,black spheres).The large yellow spheres represent the largest sphere that would fit in the cavities without touching the van der Waals atoms of the frameworks.Hydrogen atoms have been omitted.

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