title: Ligand-Assisted Liquid Crystal Templating in Mesoporous Niobium Oxide Molecular Sieves.
abstract: A systematic study of the factors governing the formation of Nb-TMS1, a niobium-based mesoporous hexagonally-packed transition metal oxide molecular sieve, is reported. The synthesis of this material was achieved through a novel ligand-assisted liquid crystal templating mechanism in which a discrete covalent bond is used to direct the templating interaction between the organic and inorganic phases. In general, the synthesis of Nb-TMS1 is more strongly affected by starting conditions such as temperature, surfactant-to-metal ratio, pH, and solvent than by temperature and time of aging after the initial hydrolysis step. The results also show that Nb-TMS1 can be synthesized under conditions which strongly disfavor the formation of micelles. This suggests that Nb-TMS1 is formed via a mechanism involving self-assembly with concomitant condensation. It was found that with increasing surfactant-to-metal ratios, new hexagonal P63/mmc (Nb-TMS2) and layered (Nb-TMS4) phases could be formed, while increasing the surfactant chain length led to a new cubic phase (Nb-TMS3). Crystals of Nb-TMS1 of up to several mm in dimensions were also grown. These crystals are larger than the biggest mesoporous crystals reported by a factor of 3 orders of magnitude. These crystals retain their structure on micelle removal by acid treatment and are thus of great interest as hosts for quantum wires.
authors.affiliation: Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139.
authors.forename: David M.
authors.initials: DM
authors.lastname: Antonelli
authors.forename: Atsushi
authors.initials: A
authors.lastname: Nakahira
authors.forename: Jackie Y.
authors.initials: JY
authors.lastname: Ying