Design of molecularly ordered framework of mesoporous silica with squared one-dimensional channels

Mesoporous silica with squared one-dimensional channels (KSW-2-type mesoporous silica), possessing a molecularly ordered framework arising from a starting layered polysilicate kanemite, was obtained through silylation of a surfactant (hexadecyltrimethylammonium, C₁₆TMA)-containing mesostructured precursor with octoxytrichlorosilane (C₈H ₁₇OSiCl₃) and octylmethyldichlorosilane (C ₈H₁₇(CH₃)SiCl₂). The presence of the molecular ordering in the silicate framework was confirmed by XRD and TEM. Octoxy groups grafted on KSW-2 can be eliminated by subsequent hydrolysis under very mild condition, and pure mesoporous silica was obtained with the retention of the kanemite-based framework. The framework is structurally stabilized by the attachment of additional SiO₄ units to the framework, and the mesostructural ordering hardly changed under the presence of water vapor. A large number of silanol groups remained at the mesopore surfaces because C ₁₆TMA ions and octoxy groups can be removed without calcination. Octylmethylsilyl groups are regularly arranged at the mesopore surface due to the molecular ordering in the silicate framework. The molecularly ordered structural periodicity originating from kanemite is retained even after calcination at 550°C, while that in the precursor without silylation disappeared. The synthetic strategy is quite useful for the design of the silicate framework of mesostructured and mesoporous materials with and without surface functional organic groups.