title: Nanostructured copper oxide on silica-zirconia mixed oxides by chemical implantation.
abstract: N,N-Dialkylcarbamato complexes of copper(II), [Cu(O(2)CNR(2))(2)] (R = All = allyl, C(3)H(5); iPr, CH(CH(3))(2)) were prepared with the aim of functionalizing silica and nanostructured silica-zirconia matrices. The mixed matrices for the grafting reactions were prepared by copolymerizing MAPTMS (methacryloxypropyltrimethoxysilane), the precursor for the silica matrix, with the zirconium tetranuclear derivative [Zr(4)O(2)(OMc)(12)] (OMc = methacrylate), the precursor for the zirconia nanoparticles. Suspension of the silica and silica-zirconia matrices in a solution of the copper dialkylcarbamate led to the functionalization of the respective substrates. The composition, microstructure, morphology, and physicochemical nature of the copper species grafted on the matrices were investigated by FTIR, X-ray photoelectron spectroscopy (XPS), EPR, X-ray absorption spectroscopy (XAS), XRD, TEM, and dinitrogen adsorption. The effect of selected experimental parameters (the nature of the copper precursor and of the matrix, grafting time, thermal treatment) on the grafting reaction was investigated. The Cu/Si ratio is increased by increasing the grafting time and the ZrO(2)-SiO(2) matrix is more reactive to attack by the carbamato complexes than either prepared or commercial SiO(2). After functionalization of the matrix, thermal treatment yielded nanostructured copper(II) oxide clusters, average diameter 12-15 nm, uniformly supported on the silica and on the silica-zirconia matrices.
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Universitá di Pisa, Pisa, via Risorgimento 35, 56126 Pisa, Italy.
authors.forename: Daniela Belli
authors.initials: DB
authors.lastname: Dell'amico
authors.forename: Helmut
authors.initials: H
authors.lastname: Bertagnolli
authors.forename: Fausto
authors.initials: F
authors.lastname: Calderazzo
authors.forename: Massimiliano
authors.initials: M
authors.lastname: D'Arienzo
authors.forename: Silvia
authors.initials: S
authors.lastname: Gross
authors.forename: Luca
authors.initials: L
authors.lastname: Labella
authors.forename: Marzio
authors.initials: M
authors.lastname: Rancan
authors.forename: Roberto
authors.initials: R
authors.lastname: Scotti
authors.forename: Bernd M
authors.initials: BM
authors.lastname: Smarsly
authors.forename: Ralf
authors.initials: R
authors.lastname: Supplit
authors.forename: Eugenio
authors.initials: E
authors.lastname: Tondello
authors.forename: Eric
authors.initials: E
authors.lastname: Wendel