Abstract
This PhD thesis is focused on the study of wet adsorption and separation properties by porous coordination polymers. We used adsorption volumetry, gas chromatography separation techniques, fluorescence spectroscopy techniques and Monte Carlo modeling to understand the mechanisms governing the adsorption of these materials. The adsorbable molecules studied are water and hydrocarbon vapors linear (pentane and n-hexane), cyclic (cyclohexane and cyclohexene) and polycyclic (anthracene). The adsorbents studied are the Prussian Blue Analogues (ABP) as well as two reference porous organometallic materials, ZIF8 and CuBTC. Among the main results provided by this work, we have shown that Prussian Blue Analogues have remarkable hydrothermal stability conferring them very promising wet adsorption properties. Among the ABPs studied, Co [CoIII (CN)6] 0.66 ⊡0.33 .5.2H2O showed adsorption and separation properties far superior to those of other ABPs. For example, it has been possible to modulate its hydrophobic / hydrophilic balance by controlling the coordination of water on the unsaturated metal center, while preserving its lipophilic character. We have also shown that this Prussian blue analogue is capable of separating mixtures of dry or very wet hydrocarbons repeatedly. On a more fundamental aspect, we have shown that the confinement of anthracene by ZIF-8, which is a porous organometallic compound with cavities of size adjusted to that of the fluorophore, could induce a complete extinction of certain absorption bands of this one.