High H2 Sorption Energetics in Zeolitic Imidazolate Frameworks

Abstract

A combined experimental and theoretical study of H2 sorption was carried out on two isostructural zeolitic imidazolate frameworks ZIFs , namely ZIF 68 and ZIF 69. The former consists of Zn2 ions that are coordinated to two 2 nitroimidazolate and two benzimidazolate linkers in a tetrahedral fashion, while 5 chlorobenzimidazolate is used in place of benzimidazolate in the latter compound. H2 sorption measurements showed that the two ZIFs display similar isotherms and isosteric heats of adsorption Qst . The experimental initial H2 Qst value for both ZIFs was determined to be 8.1 kJ mol 1, which is quite high for materials that do not contain exposed metal centers. Molecular simulations of H2 sorption in ZIF 68 and ZIF 69 confirmed the similar H2 sorption properties between the two ZIFs, but also suggest that H2 sorption is slightly favored in ZIF 68 with regards to uptake at 77 K 1.0 atm. This work also presents inelastic neutron scattering INS spectra for H2 sorbed in ZIFs for the first time. The spectra for ZIF 68 and ZIF 69 show a broad range of intensities starting from about 4 meV. The most favorable H2 sorption site in both ZIFs corresponds to a confined region between two adjacent 2 nitroimidazolate linkers. Two dimensional quantum rotation calculations for H2 sorbed at this site in ZIF 68 and ZIF 69 produced rotational transitions that are in accord with the lowest energy peak observed in the INS spectrum for the respective ZIFs. We found that the primary binding site for H2 in the two ZIFs generates high barriers to rotation for the adsorbed H2, which are greater than those in several metal organic frameworks MOFs which possess open metal sites. H2 sorption was also observed for both ZIFs in the vicinity of the nitro groups of the 2 nitroimidazolate linkers. This study highlights the constructive interplay of experiment and theory to elucidate critical details of the H2 sorption mechanism in these two isostructural ZIF