A route to high surface area, porosity and inclusion of large molecules in crystals

One of the outstanding challenges in the field of porous materials is the design and synthesis of chemical structures with exceptionally high surface areas(1). Such materials are of critical importance to many applications involving catalysis, separation and gas storage. The claim for the highest surface area of a disordered structure is for carbon, at 2,030 m(2) g(-1) (ref. 2). Until recently, the largest surface area of an ordered structure was that of zeolite Y, recorded at 904 m(2) g(-1) (ref. 3). But with the introduction of metal-organic framework materials, this has been exceeded, with values up to 3,000 m(2) g(-1) (refs 4-7). Despite this, no method of determining the upper limit in surface area for a material has yet been found. Here we present a general strategy that has allowed us to realize a structure having by far the highest surface area reported to date. We report the design, synthesis and properties of crystalline Zn4O(1,3,5-benzenetribenzoate)(2), a new metal-organic framework with a surface area estimated at 4,500 m(2) g(-1). This framework, which we name MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules-attributes not previously combined in one material.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62609/1/nature02311.pd

Raman spectra of hydrogen and deuterium adsorbed on a metal-organic framework

Abstract The Raman spectra of H 2 and D 2 adsorbed on metal-organic framework-5 at various pressures (H 2 : 12.8 and 30.3 bar; D 2 : 2.2-24.5 bar) and temperatures (H 2 : 298 K; D 2 : 40-300 K) have been recorded. The shifts observed in the vibrational modes of the gases indicate that physisorption is responsible for the attractive interactions between the gas and the framework; these interactions are larger with respect to those detected for carbon materials. Ó 2005 Elsevier B.V. All rights reserved. The lack of a suitable and cost effective means of storing hydrogen Understanding the intermolecular interactions responsible for gas sorption (e.g., hydrogen) in solids (e.g., MOFs, carbon based materials, etc.) is fundamentally important to the development of new materials with improved gas sorption properties and geometries. The perturbation of the intramolecular potential resulting from intermolecular interaction with an adsorbing surface suggests that vibrational spectroscopy in general, and especially Raman spectroscopy, may turn out to be a useful technique to investigate the physical phenomena that take place because of these interactions Let us consider a pure diatomic gas: the intermolecular interactions (attractive and repulsive) with other gas molecules perturb the intramolecular potentia