We investigated emulsions stabilized with particles of layered hexaniobate, known as a semiconductor photocatalyst, and photocatalytic degradation of dyes in the emulsions. Hydrophobicity of the niobate particles was adjusted with the intercalation of alkylammonium ions into the interlayer spaces to enable emulsification in a toluene-water system. After the modification of interlayer space with hexylammonium ions, the niobate stabilized water-in-oil (w/o) emulsions in a broad composition range. Optical microscopy showed that the niobate particles covered the surfaces of emulsion droplets and played a role of emulsifying agents. The niobate particles also enabled the generation of oil-in-water (o/w) emulsions in a limited composition range. Modification with dodecylammonium ions, which turned the niobate particles more hydrophobic, only gave w/o emulsions, and the particles were located not only at the toluene-water interface but also inside the toluene continuous phase. On the other hand, interlayer modification with butylammonium ions led to the formation of o/w emulsions. When porphyrin dyes were added to the system, the cationic dye was adsorbed on niobate particles at the emulsion droplets whereas the lipophilic dye was dissolved in toluene. Upon UV irradiation, both of the dyes were degraded photocatalytically. When the cationic and lipophilic porphyrin molecules were simultaneously added to the emulsions, both of the dyes were photodecomposed nonselectively.
Layered niobate K4Nb6O17 became compatible to organic solvents through grafting octadecyltrimethoxysilane onto the niobate layers. The silylated niobate was stably dispersed in chloroform and finitely swelled in toluene whereas the niobate intercalated with dodecylammonium ions was settled out in both the solvents. Colloids of the silylated niobate dispersed in chloroform exhibited lyotropic liquid crystallinity at high niobate concentrations.
Layered hexaniobate K4Nb6O17 was modified with dodecylammonium ions and octadecyltrimethoxysilane molecules, which were held in the interlayer spaces by electrostatic interactions and covalent attachment to the layers, respectively. Interlayer spacing of the niobate was expanded by incorporation of the bulky organic species. Vapor adsorption isotherms of benzene and water indicated hydrophobic interlayer microenvironments of the organically modified niobates. Both of the modified niobates fairly adsorbed phenol dissolved in water. The photocatalytic activity of hexaniobate allowed the organically modified materials to photocatalytically decompose phenol upon UV irradiation. Decomposition time courses and quantitative analysis of phenol present in the system indicated that the phenol molecules adsorbed on the niobates were preferentially degraded. XRD and IR analyses of the modified niobates indicated that the silylated niobate was more durable than the ion-exchanged sample; the former kept the structure during the photocatalytic process while the latter was partly collapsed.
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