Structural Changes of Hierarchically Nanoporous Organosilica/Silica Hybrid Materials by Pseudomorphic Transformation

Herein, it is reported how pseudomorphic transformation of divinylbenzene (DVB)‐bridged organosilica@controlled pore glasses (CPG) offers the possibility to generate hierarchically porous organosilica/silica hybrid materials. CPG is utilized to provide granular shape/size and macroporosity and the macropores of the CPG is impregnated with organosilica phase, forming hybrid system. By subsequent pseudomorphic transformation, an ordered mesopore phase is generated while maintaining the granular shape and macroporosity of the CPG. Surface areas and mesopore sizes in the hierarchical structure are tunable by the choice of the surfactant and transformation time. Two‐dimensional magic angle spinning (MAS) NMR spectroscopy demonstrated that micellar‐templating affects both organosilica and silica phases and pseudomorphic transformation induces phase transition. A double‐layer structure of separate organosilica and silica layers is established for the impregnated material, while a single monophase consisting of randomly distributed T and Q silicon species at the molecular level is identified for the pseudomorphic transformed materials.