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Abstract: ZIF-76, Zn(Im) x (5-ClbIm) y (Im=imidazolate, 5-ClbIm=5-chlorobenzimidazolate), is, among the known ZIF structures, one of the few materials that combine a relatively large pore aperture with a large pore volume. Moreover, it is thermally stable up to 400°C and can be stored under ambient atmosphere without undergoing a measurable degradation. ZIF-76, therefore, appears to be an interesting material for applications in adsorption and separation. The published synthesis protocol leads to very low yields and is, thus, not applicable on a larger scale . In this work, we have succeeded in preparing ZIF-76 in suitable yields by changing the solvent and adding NaOH to the synthesis mixture. The addition of the base increases the yield and leads to smaller crystal sizes, by favoring nucleation over crystal growth. By using the same synthesis strategy, four new isomorphs of ZIF-76 were obtained, with different substituents on the benzimidazole ligand (Me, Br and NO2) and different metal sources (Co and Zn). All the samples were tested in the adsorption and separation of CO2/CH4 in order to highlight the influence of the linker and of the metal center on the adsorption/separation properties. [Copyright &y& Elsevier]

Water adsorption in the large pore ( lp_empty ) form of Ga-MIL-53 was studied by TGA, DSC and in situ XRD and FTIR at 298 K. The large pore form can be stabilized at room temperature after activation under vacuum at 553 K. The isotherm of water adsorption in this large pore form (pore dimensions: 1.67 × 1.33 nm) is very similar to that measured on the narrow pore ( np_empty ) form (pore dimensions: 1.97 × 0.76 nm). Such a similarity is rather unusual given that the pore sizes of these two phases are very different. In order to understand the origin of this effect in situ XRD and FTIR measurements were particularly helpful. It was found that the adsorption of even small amount of water (0.05 mol per Ga atom at 0.2 hPa) in the large pore form of Ga-MIL-53 transforms ca. 50% of the solid into a narrow pore int phase, which is assumed to be present as a shell around the lp_empty core. Additional water molecules adsorbed at higher pressures do not interact with the parent lp_empty phase but with the narrow pore int phase. The phase transformations were confirmed by FTIR revealing significant band displacements in the corresponding pressure ranges. Such easy pore shrinking which occurs at very low water pressure (<0.2 hPa) can have undesirable consequences in working conditions, as for example in separation adsorption processes, because the large pore structure of Ga-MIL-53 can be preserved only under anhydrous conditions. [ABSTRACT FROM AUTHOR]