LIGAND-ASSISTED LIQUID-CRYSTAL TEMPLATING IN MESOPOROUS NIOBIUM OXIDEMOLECULAR-SIEVES

A systematic study of the factors governing the formation of Nb-TMS1, a niobium-based mesoporous hexagonally-packed transition metal oxide m olecular sieve, is reported. The synthesis of this material was achiev ed through a novel ligand-assisted liquid crystal templating mechanism in which a discrete covalent bond is used to direct the templating in teraction between the organic and inorganic phases. In general, the sy nthesis of Nb-TMS1 is more strongly affected by starting conditions su ch as temperature, surfactant-to-metal ratio, pH, and solvent than by temperature and time of aging after the initial hydrolysis step. The r esults also show that Nb-TMS1 can be synthesized under conditions whic h strongly disfavor the formation of micelles. This suggests that Nb-T MS1 is formed via a mechanism involving self-assembly with concomitant condensation. It was found that with increasing surfactant-to-metal r atios, new hexagonal P63/mmc (Nb-TMS2) and layered (Nb-TMS4) phases co uld be formed, while increasing the surfactant chain length led to a n ew cubic phase (Nb-TMS3). Crystals of Nb-TMS1 of up to several mm in d imensions were also grown. These crystals are larger than the biggest mesoporous crystals reported by a factor of 3 orders of magnitude. The se crystals retain their structure on micelle removal by acid treatmen t and are thus of great interest as hosts for quantum wires.