Nanostructured copper oxide on silica-zirconia mixed oxides by chemical implantation

A new route to chemical implantation of copper(II) N,N-dialkylcarbamato complexes on silica and nanostructured silica–zirconia matrices and subsequent thermal treatment (see scheme) is an efficient method of functionalizing the oxide matrices with nanostructured CuO. The materials have been characterized thoroughly and the effect of selected experimental parameters on the grafting reaction was investigated. N,N-Dialkylcarbamato complexes of copper(II), [Cu(O2CNR2)2] (R=All=allyl, C3H5; iPr, CH(CH3)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 [Zr4O2(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 ZrO2–SiO2 matrix is more reactive to attack by the carbamato complexes than either prepared or commercial SiO2. 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.