Composition, structure, and luminescence of montmorillonites saturated with different aggregates of methylene blue.

The distribution of various aggregates (dimers, trimers, and tetramers) of methylene blue (MB) formed in aqueous solution at various concentrations of dye has been calculated using the equilibrium aggregation constants betaq. Two montmorillonite samples with different cation exchange capacities, surface areas, and interlayer distances d001, Na-SWy, and Ca-Cheto, were saturated with methylene blue (MB) solutions with various ratios between monomers and higher aggregates of dye. The total amount of MB in the intercalated montmorillonite samples (MB-SWy and MB-Cheto) increases with increasing concentration of dye in water solutions, i.e., with increasing aggregates/monomers ratio of MB in water solution. In all intercalated montmorillonite samples with methylene blue except guest qth aggregate cations [MBqq+] low contents of Na+ (in MB-SWy) and Ca2+ (in MB-Cheto) cations were also determined. A very good positive correlation between the basal spacing d001 and the MB/montmorillonite molar ratio was revealed for saturated MB-montmorillonite samples. Structural analysis using a combination of diffraction data with molecular modeling revealed the differences in the interlayer arrangement of MB guests in MB-SWy and MB-Cheto intercalates. Also, fluorescence measurements showed the strong effect of the silicate layer charge on the spectroscopic behavior of MB guests intercalated in montmorillonite. Methylene blue exhibits a certain luminescence in MB-SWy samples with cation exchange capacity 0.80 meq g-1 and almost no luminescence in MB-Cheto samples with higher cation exchange capacity 1.50 meq g-1.