Synthesis of porous silica with hierarchical structure directed by a silica precursor carrying a pore-generating cage

We have obtained a new class of porous silica with good structural order and additional corrugated nanopores clustered around the primary mesopores from the co-condensation of TEOS and adamantylphenol-grafted trimethoxysilane (adam-graft SQ) using a triblock Pluronic P123 (EO20PO70EO20, M-w = 5800) copolymer as a structure-directing agent. Thermally activated removal of pore-generating moieties (i.e., adamantylphenol groups) in adam-graft SQ involves the generation of secondary micro-to-small mesopores, while the block copolymer template generates 2D-hexagonal mesopores. We found that the mesostructural characteristics and the generation of secondary indented pores right next to the mesopores can be tailored by the addition order of the two silica precursors (TEOS and adam-graft SQ), varying the molar ratio between TEOS and adam-graft SQ in the starting sol mixture, and the degree of silica polymerization. The increase in the hexagonal unit cell parameters is attributed to the increment of pore size originating from the removal of adamantylphenol moieties. It is believed that the hydrophobicity of adamantylphenol groups plays a key role in its selective incorporation into the region near the PPO core blocks and the subsequent generation of corrugated pores along the silica channels resulting in the increase of pore diameter.