Alkoxysilylation of Ti-MWW lamellar precursors into interlayer pore-expanded titanosilicates

Silylation of Ti-MWW lamellar precursor and subsequent calcination constructed an interlayer expanded structure, leading to novel titanosilicates with large pores. The silylating agents suitable for pore expansion were diethoxydimethylsilane, trimethylethoxysilane and triethoxymethylsilane containing methyl groups, which inhibited the intermolecular condensation of silanes effectively. In contrast to well-known 3D Ti-MWW with only medium pores of 10-membered rings, the silylation led to new crystalline structures with more open pores by ca. 2.5 Å, as evidenced by the shift of layer-related diffractions to the lower-angle region in XRD patterns and the enlarged interlayer pores in HRTEM images. The interlayer expanded Ti-MWW was prepared readily from the corresponding hydrothermally synthesized precursors with a wide range of Ti contents (Si/Ti = 20-100). In addition, the pore expansion by silylation was realized under mild acid conditions with 0.1 M HNO₃. The interlayer expanded Ti-MWW exhibited 3-7 times higher turnover number than 3D Ti-MWW in the oxidation of cyclohexene with H₂O₂.