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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]

The influence of sodium cations content in zeolite Beta crystals of different sizes (between 200 nm and 2 μm) on the adsorption of pollutants (dioxin and polychlorobenzene) is investigated. In this study, protons which balance the negative charge of the zeolitic framework are partially replaced by sodium cations. Chemical, structural and textural analyses performed on the exchanged crystals indicate that the exchange rates reached 75-80 % and that the structure of zeolites is preserved. Adsorptions of pollutants in zeolite Beta samples were successfully carried out using 1,2-dichlorobenzene (gas phase) and 2,3-DiChloroDibenzo- p-Dioxin: 2,3-DCDD (liquid phase) but reveal different behaviors. Indeed, all samples adsorb the same amount (around 7 molecules) of 1,2-dichlorobenzene per unit-cell of zeolite, whereas the dioxin adsorption amounts increase with the amount of sodium cations. Compared to their protonic forms, the dioxin adsorption capacities were multiplied by a factor of 1.3 for the sodium exchanged small crystals (size between 200 nm and 1 μm) and by a factor of 4 for the sodium exchanged microcrystals (size between 1 and 2 μm) for an equilibrium concentration of 2,3-DCDD of 0.5 mmol/L in both cases. [ABSTRACT FROM AUTHOR]