Hydrothermal and Postsynthesis Surface Modification of Cubic, MCM-48, and Ultralarge Pore SBA-15 Mesoporous Silica with Titanium

We describe the introduction of titanium centers to cubic MCM-48 and SBA-15 mesoporous silica by hydrothermal and postsynthetic grafting techniques. MCM-48 was hydrothermally prepared with a gemini surfactant that favors the cubic phase and leads to a high degree of long-range pore ordering. This phase was chosen due to its high surface area (1100−1300 m2/g) and its three-dimensional, bicontinuous pore array. SBA-15, synthesized with a block copolymer template under acidic conditions, has a surface area from 600 to 900 m2/g and an average pore diameter of 69 Å, compared to 24−27 Å for MCM-48. Alkoxide precursors of titanium were used to prepare samples of Ti-MCM-48 and Ti-SBA-15. We have detailed the bulk and molecular structure of both the silica framework and the local bonding environment of the titanium ions within each matrix. X-ray powder diffraction and nitrogen adsorption shows the pore structure is maintained despite some shrinkage of the pore diameter at high Ti loadings by grafting methods. UV−visible and Raman spectroscopy indicate that grafting produces the least amount of Ti−O−Ti bonds and instead favors isolated tetrahedral and octahedral titanium centers. High-resolution photoacoustic FTIR spectra demonstrated the presence of intermediate range order within the silicate walls of MCM-48, established the consumption of surface silanols to form Si−O−Ti bonds by grafting, and resolved the characteristic IR absorbance at 960 cm-1, occurring in titanium silicates, into two components. All three spectroscopic techniques, including in situ Raman, reveal the reactive intermediates formed when the materials are contacted with hydrogen peroxide.