FINAL REPORT

Abstract

Hydrogen storage systems based on the readily reversible adsorption of H{sub 2} in porous materials have a number of very attractive properties with the potential to provide superior performance among candidate materials currently being investigated were it not for the fact that the interaction of H{sub 2} with the host material is too weak to permit viable operation at room temperature. Our study has delineated in quantitative detail the structural elements which we believe to be the essential ingredients for the future synthesis of porous materials, where guest-host interactions are intermediate between those found in the carbons and the metal hydrides, i.e. between physisorption and chemisorption, which will result in H{sub 2} binding energies required for room temperature operation. The ability to produce porous materials with much improved hydrogen binding energies depends critically on detailed molecular level analysis of hydrogen binding in such materials. However, characterization of H{sub 2} sorption is almost exclusively carried by thermodynamic measurements, which give average properties for all the sites occupied by H{sub 2} molecules at a particular loading. We have therefore extensively utilized the most powerful of the few molecular level experimental probes available to probe the interactions of hydrogen with porous materials, namely inelastic neutron scattering (INS) spectroscopy of the hindered rotations of the hydrogen molecules adsorbed at various sites, which in turn can be interpreted in a very direct way in by computational studies. This technique can relate spectral signatures of various H{sub 2} molecules adsorbed at binding sites with different degrees of interaction. In the course of this project we have synthesized a rather large number of entirely new hybrid materials, which include structural modifications for improved interactions with adsorbed hydrogen. The results of our systematic studies on many porous materials provide detailed information on the effects on hydrogen binding from framework modifications, including charged frameworks and extraframework cations, from reduction in pore sizes, functionalization of the organic linking group, and most importantly, that of the various types of metal sites. We provided a clear demonstration that metal sites are most effective if the metal is highly undercoordinated, open and completely accessible to the H{sub 2} molecule, a condition which is not currently met in MOFs with intra-framework metals. The results obtained from this project therefore will give detailed direction to efforts in the synthesis of new materials that can reach the goal of a practical sorption based hydrogen storage material.