Molecular manipulation of two- and three-dimensional silica nanostructures by alkoxysilylation of a layered silicate octosilicate and subsequent hydrolysis of alkoxy groups

Dai Mochizuki, Atsushi Shimojima, Takeshi Imagawa, Kazuyuki Kuroda

Research output: Contribution to journalArticle

69 Citations (Scopus)

Abstract

A novel methodology for constructing molecularly ordered silica nanostructures with two-dimensional (2-D) and three-dimensional (3-D) networks has been developed by using a stepwise process involving silylation of a layered silicate octosilicate with alkoxytrichlorosilanes [ROSiCl3, R = alkyl] and subsequent reaction within the interlayer spaces. Alkoxytrichlorosilanes react almost completely with octosilicate, bridging two closest Si-OH (or -O-) sites on the silicate layers, to form new five-membered rings. The unreacted functional groups, Si-Cl and Si-OR, are readily hydrolyzed by the posttreatment with a water/dimethyl sulfoxide (DMSO) or water/acetone mixture, leading to the formation of two types of silicate structures. The treatment with a water/DMSO mixture produced a unique crystalline 2-D silicate framework with geminal silanol groups, whereas a water/acetone mixture induced hydrolysis and subsequent condensation between adjacent layers to form a new 3-D silicate framework. The 2-D structure is retained by the presence of DMSO molecules within the swelled interlayer spaces and is transformed to a 3-D silicate upon desorption of DMSO. The structural modeling suggests that both of the 3-D silicates contain new cagelike frameworks where solvent molecules are trapped even at high temperature (up to 380°C, in the case of acetone). Both 2-D and 3-D silica structures are quite different from known layered silicates and zeolite-like materials, indicating the potential of the present approach for precise design of various silicate structures at the molecular level.

Original languageEnglish
Pages (from-to)7183-7191
Number of pages9
JournalJournal of the American Chemical Society
Volume127
Issue number19
DOIs
Publication statusPublished - 2005 May 18

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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