Synthesis and Characterization of Octahedral Molecular Sieves (OMS-2) Having the Hollandite Structure

Hollandite and cryptomelane materials have been prepared using two different methods. Octahedral molecular siev (OMS) having the 2x2 hollandite structure with a one-dimensional pore diameter of 4.6 {Angstrom} Synthetic cryptomelane or OMS-2 can be formed by refluxing or autoclaving an acidic solution of KMnO{sub 4} and Mn{sup 2+}. Temperature, pH, and countercation are important synthetic parameters. The hollandite formed shows thermal stability up to 600 {degrees}C. OMS-2 formed by oxidation of Mn{sup 2+} under basic conditions and calcined at higher temperature (200-800 {degrees}C) is thermally stable up to 800 {degrees}C. X-ray powder diffraction and electron diffraction patterns have been simulated that show good agreement with experimental data supporting a tetragonal crystal system in the I4/m space group. Hollandites were also prepared in the presence of other transition-metal ions such as Cu{sup 2+} and Fe{sup 3+}. Electron paramagnetic resonance (EPR) data show that OMS-2 materials synthesized in the presence of Cu{sup 2+} and Fe{sup 3+} contain nonexchangeable Mn{sup 2+}. EPR data for Cu-OMS-2 showed a characteristic six-line pattern with a g value of 2.0 and A value of 85 G indicative of octahedral Mn{sup 2+} coordination. The Mn{sup 2+} EPR peaks in Fe-OMS-2 showed similar g and A values. EPR spectra, ion-exchange data, X-ray diffraction patterns, and the theoretical simulations of diffraction data suggest that Cu{sup 2+} and Fe{sup 3+} are located in the tunnels of OMS-2. 29 refs., 8 figs., 3 tabs.