Influence of MIL-101 doping by ionic clusters on hydrogen storage performance up to 1900 bar.

Ultra-high-pressure hydrogen-storage performance (up to 1900 bar) was investigated for mesoporous chromium terephthalate MIL-101 and its inclusion compounds containing ionic clusters [Re(4)S(4)F(12)](4-) and [SiW(11)O(39)](7-) within the porous framework. The maximum specific hydrogen uptake values (total) for MIL-101 are 12.3 (at 81) and 7.2 wt. % (at 293 K). Such unique measurement conditions allowed us to identify the density of the absorbed hydrogen directly from the excess sorption isotherm curves. The corresponding density values were found to be almost comparable at low temperature, but significantly different at ambient temperature, which indicated an increase of more than double in the number of hydrogen binding sites in the case of the inclusion compounds with rhenium clusters.

Methane sorption and structural characterization of the sorption sites in Zn2(bdc)2(dabco) by single crystal X-ray crystallography.

Sorption isotherms of methane in Zn(2)(bdc)(2)(dabco) are measured up to a pressure of 35 bar in the temperature range between 198-296 K. The methane sorption measurements at 296 K showed an uptake of 137 cm(3) cm(-3) at 35 bar. The enthalpy of methane adsorption for Zn(2)(bdc)(2)(dabco) estimated by the virial equation is 13.6 kJ mol(-1) at zero coverage. X-ray structure analysis of methane-adsorbed Zn(2)(bdc)(2)(dabco) by synchrotron radiation at 90 K revealed that methane molecules occupy three independent sorption sites (A, B, and C) with a stoichiometry of Zn(2)(bdc)(2)(dabco) x 6.69 CH(4), which is consistent with the results of the gas sorption measurements at 198 K. In a cavity, eight symmetry-related methane sorption sites A are located near the {Zn(2)(CO(2))(4)} paddle-wheel units, while four symmetry-related methane sorption sites B are near the center of the small windows along the a and b axes. Both A and B sites are half-occupied. Methane molecules occupying sites A are not only in van der Waals contact with the paddle-wheel units, but also interact with the phenyl rings of bdc ligands through partial pi-HC interactions. Methane molecules in B sites interact with the side of the phenyl rings through van der Waals interaction. The site C, located at the center of the cavity, is a secondary sorption site; methane molecules occupying sites C are in van der Waals contact with those in sites A and B.