Microporous coordination polymers (MCPs) are most typically built from rigid ligands and arrays of metals/metal clusters resulting in the formation of crystalline materials; in many cases these materials are highly porous. The chemical and structural features are easily controlled in MCPs thus offering significant potential for their development as application-specific, high performance materials. However, commercial applications of MCPs have been slow to develop and one often cited barrier to applications for some MCPs is their instability against moisture. This thesis focuses on application-oriented investigation of the interaction between water and MCPs: MCPs have been intensively studied as practical industrially viable sorbents for gas dehumidification, MCP porosity evolution during water degradation has been elucidated by positronium annihilation lifetime spectroscopy (PALS), and a hybrid polymer@MCP composite with increased water stability has been studied.MCPs are demonstrated here to be efficient desiccants for the dehumidification of air and comparison of their capacity, regenerability and efficiency with commercial activated alumina is conducted. Complete regeneration using dry air with mild heating is achieved. The achievement of high water adsorption capacity coupled to gentle regeneration indicates that gas dehumidification may be an important application for MCPs.The details of MCPs structural collapse caused by water with regard to pore size evolution are acquired by incorporating a flow-through system in tandem with PALS. From the decrease in porosity, we have observed an induction period for water degradation of some Zn4O-based MCPs that signals much greater stability than commonly believed to be possible. The sigmoidal trend in the degradation curve of unfunctionalized MCPs caused by water vapor has been established. The water sensitivity of Zn4O-based MCPs is found to be structure and history dependent.A hybrid polymer@MCP architecture is examined, which interfaces hard (crystalline) MCP, MOF-5, and soft (amorphous) polymers, polystyrene, to form polystyrene@MOF-5 in which polystyrene chains are uniformly tethered to the outer shell of MOF-5. Control over the position of polymer initiation and the thickness of the polymer coating is achieved by IRMOF-3@MOF-5 core-shell arrangement. The polystyrene@MOF-5 demonstrates an increase in the kinetic stability when subjected to humid environments.
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Water Interaction with Microporous Coordination Polymers: Energy Efficient Dehumidification, Antimatter Probing and Polymer Coating.