| The objective of this thesis is to describe the preparation and investigation of a new class of proton-conducting membrane materials, namely, nanoporous colloidal membranes whose proton conductivity results from the nanopore surface modification with organic molecules carrying acid functionalities. Both the proton transport and ion transport were studied in nanoporous silica colloidal crystals that were surface modified with sulfonic groups.;Second, the proton transport in free-standing assemblies of surface-sulfonated silica nanospheres, either randomly packed or self-assembled into a close-packed arrangement, were studied. It was demonstrated that colloidal assemblies prepared using surface-sulfonated silica nanospheres posses proton conductivity that depends on the ordering of the material, temperature and relative humidity. Based on the comparison between the close-packed and disordered assemblies made of the same spheres, we conclude that the increase in structural organization of the self-assembled colloidal materials leads to increased proton conductivity and better water retention.;Next free-standing colloidal membranes with a relatively large area and no mechanical defects were prepared by sintering silica colloidal films. The sintered membranes were then surface rehydroxylated, which restores the surface silanol groups, and then can be chemically modified.;Finally, sintered self-assembled nanoporous silica colloidal crystals were modified with poly(sulfopropyl-methacrylate) (pSPM) and poly(stryrenesulfonic acid) (pSSA) brushes which were covalently attached to the nanopore surface. The resulting robust membranes possess temperature and humidity-dependent proton conductivity. Also proton conductive membranes were prepared by self-assembly of silica nanospheres modified with pSPM and pSSA brushes of different thickness. These membranes showed a slightly higher proton conductivity and water uptake but poor mechanical properties.;First, the transport of ions was studied through sulfonated silica colloidal films that were supported on platinum electrodes using cyclic voltammetry. The surface of self-assembled nanoporous silica colloidal crystalline films was sulfonated using 1,3-propanesultone. We found that the flux of anions through the sulfonated colloidal films is reduced, while the flux of cations is increased, compared to the unmodified colloidal films. |
