title: Mesoporous Zirconium Phenylenesiliconate-phosphonate Hybrids with Ordered Lamellar Nanostructures.
abstract: Novel ordered lamellar mesostructure pZrPS-2 was hydrothermally prepared by using zirconium propoxide and 4-(EtO)2OPC6H4Si(OEt)3 (pPPS-E), which was hydrolyzed to organic building units substituted with both siliconate and phosphonate groups, in the presence of Cn TAB and TMAOH. The pZrPS-2 materials were obtained at a Zr/PPS ratio of 2 or higher and the basal spacing was increased by using a longer-chain surfactant (n = 12-18). Removal of the occluded surfactants at 300 °C resulted in retention of the lamellar structure with negligible shrinkage of the interlayer distance. Nitrogen adsorption studies revealed the ordered mesoporous nature of pZrPS-2 with a pore diameter of approximately 2 to 3 nm. The lamellar structure is assumed to be composed of layers that include zirconia-based crystalline nanodomains and interlayer pillars mainly based on PPS units. Although lamellar structures with the same crystalline phase also formed when no surfactant was added or when the meta isomer of PPS was used, no mesoporous materials were obtained except pZrPS-2. A possible schematic model to elucidate these results is also proposed.
authors.affiliation: Department of Applied Chemistry, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan). k-maeda@cc.tuat.ac.jp.
authors.forename: Kazuyuki
authors.initials: K
authors.lastname: Maeda
authors.affiliation: Department of Applied Chemistry, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan).
authors.forename: Hiroki
authors.initials: H
authors.lastname: Kobayashi
authors.affiliation: Department of Applied Chemistry, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan).
authors.forename: Kaku
authors.initials: K
authors.lastname: Oguro
authors.affiliation: Department of Applied Chemistry, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan).
authors.forename: Masato
authors.initials: M
authors.lastname: Otsu
authors.affiliation: Department of Applied Chemistry, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan).
authors.forename: Atsushi
authors.initials: A
authors.lastname: Kondo
authors.affiliation: Research Center for Science and Technology, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan).|EM Application Department, EM Business Unit, JEOL Ltd., Akishima, Tokyo 196-8558 (Japan).
authors.forename: Tei
authors.initials: T
authors.lastname: Maki
keywords: lamellar mesostructures; mesoporous materials; metal phosphonates; organic-inorganic hybrid composites; organosilicas