Surfactant mediated control of pore size and morphology for molecularly ordered ethylene-bridged periodic mesoporous organosilica

A series of ethylene-containing mesoporous organosilica materials were fabricated via surfactant-mediated assembly of 1,2-bis(triethoxysilyl)ethylene (BTEE) organosilica precursor using alkyltrimethylammonium bromide (CnTAB) surfactants with different alkyl chain length (n=12, 14, 16, 18) as supramolecular templates. The presence of molecularly ordered ethylene groups in the resulting periodic mesoporous organosilica (PMO) materials was confirmed by XRD data along with 29Si and 13C MAS NMR analysis. Additional characterization techniques, namely nitrogen sorption, TEM, and TGA, confirmed the structural ordering and thermal stability of the molecularly ordered ethylene-bridged PMOs. The PMOs exhibit molecular-scale ordering (with a periodicity of 5.6 A) within the organosilica framework and tunable pore size, which depending on the alkyl chain length of the surfactant templates, varied in the range 23-41 A. Furthermore, depending on the alkyl chain length of the templates, the particle morphology of the PMOs gradually changed from monodisperse spheres (for C12TAB) to rod or cakelike particles (for C14TAB) and elongated ropelike particles for longer chain surfactants. Variations in the surfactant chain length therefore allowed control of both the pore size and particle morphology without compromising molecular-scale or structural ordering. The reactivity of ethylene groups was probed by bromination, which demonstrated the potential for further functionalization of the PMOs.