Li-Crown ether complex inclusion in MOF materials for enhanced H_2 volumetric storage capacity at room temperature

摘要

The organometallic Li-Crown ether species, formed by the complexation of lithium cation with the hydrophobic 18Crown6 ether, has been included in three Metal-Organic-Frameworks (MOF) structures with different pore size: Cr-MIL-101, Fe-MIL100 and Ni-MOF-74. X-ray powder diffraction, thermogravimetric analysis, proton nuclear magnetic resonance, infrared spectroscopy and inductively coupled plasma atomic emission spectroscopy measurements have proved the successful incorporation of the organometallic units to the three MOFs without altering their crystalline structure. Hydrogen adsorption properties of the post-synthesis modified materials have been evaluated in a wide temperature (77-298 K) and pressure (1-170 bar) range conditions. The post-synthetic modification method used based on the MOF impregnation with a Li-Crown ether complex solution produced a partial pore blocking effect on the microporous Ni-MOF-74, reducing its hydrogen adsorption capacity. However, the inclusion of the crown-ether and particularly the Li-Crown ether complex resulted in an increase of the volumetric hydrogen adsorption capacity at room temperature for Cr-MIL101 and Fe-MIL-100, due to the pore volume reduction, higher confinement of H-2 molecules in the cavities and the formation of new specific binding sites for H-2 molecules. The inclusion of Li-Crown ether complex also enhances the H-2 interaction with the mesoporous MOF structures, attributed to the additional electrostatic interactions produced by the presence of Li+ ions complexed to the crown ether molecules. Further work following this strategy to improve hydrogen adsorption capacity of mesoporous MOFs at room temperature should be extended to other MOF materials, checking its influence on their capacity for gas separation purposes. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.