A spectroscopic study on the adsorption of cationic dyes into mesoporous AlMCM-41 materials

Mesoporous materials loaded with dyes are of interest with respect to novel optical applications. The spectral behaviors of some dyes in these materials are considerably affected by the presence of surfactants. A comparative study has been carried out on the adsorption of the methylene blue, rhodamine 6G and thionine dyes into a surfactant-free and surfactant-containing mesoporous AlMCM-41. The ion exchange method has been employed for incorporation of the dye molecules into the structure of MCM-41. The exchangeable sites in the MCM-41 were generated prior to dye loading by isomorphous substitution of aluminum for silicon in the structure of the mesoporous material during the synthesis procedure. Diffuse reflectance measurements indicate adsorption of methylene blue and rhodamine 6G dye molecules into AlMCM-41 taken place via ion exchange at room temperature. The spectra show presence of monomer and dimer aggregates of the dyes established into the pores and surface of AlMCM-41. The ratio of dimer to monomer forms of rhodamine 6G incorporated in the surfactant-free and surfactant-containing AlMCM-41 is about one which is higher than those observed in aqueous solutions. The surfactant-containing AlMCM-41 induced destabilization and decomposition of methylene blue while uploading the dye. Degradation of this dye produces intermediate species identified as demethylated forms of methylene blue adsorbed on AlMCM-41. Our experiments revealed that kinetics of ion exchange for thionine dye is very slow at room temperature, but it become faster at higher temperatures. The spectral properties of thionine in AlMCM-41 are close to that of thionine in an aqueous solution, possibly due to high pore space in a mesoporous molecular sieve. No adsorption of thionine was observed for surfactant-containing AlMCM-41 even at higher temperatures.