title: Design of layered silicate by grafting with metal acetylacetonate for high activity and chemoselectivity in photooxidation of cyclohexane.
abstract: We succeeded in the immobilization of Ti(IV) acetylacetonate onto interlayer surfaces of a layered silicate HUS-2 (Hiroshima University Silicate-2, Si20O40(OH)4·4[C5H14NO]) and investigated the photocatalytic acitivity of Ti-incorporated HUS-2 toward the partial oxidation of cyclohexane to cyclohexanol and cyclohexanone under solar light irradiation. XRD, SEM/EDX, (13)C CP and (29)Si MAS NMR and UV-vis measurements of Ti-incorporated HUS-2 confirmed that the isolated tetrahedral Ti species were homogeneously immobilized onto silicate sheets via Si-O-Ti covalent bond and acetylacetonate ligands were removed after calcination. Ti-incorporated HUS-2 showed ca. 100% selectivity for partial cyclohexane oxidation and considerably higher yields (cyclohexanol and cyclohexanone) than TS-1, a typical Ti-containing zeolite. Higher yields were obtained when the calcined Ti-incorporated HUS-2 with a larger amount of the grafted Ti were used.
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University , 1-4-1 Kagamiyama, Higashi-Hiroshima 739-8527, Japan.
authors.forename: Nao
authors.initials: N
authors.lastname: Tsunoji
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Ide
authors.forename: Yuya
authors.initials: Y
authors.lastname: Yagenji
authors.forename: Masahiro
authors.initials: M
authors.lastname: Sadakane
authors.forename: Tsuneji
authors.initials: T
authors.lastname: Sano