title: A generalized method toward high dispersion of transition metals in large pore mesoporous metal oxide/silica hybrids.
abstract: A series of transition metal acetylacetonates and acetates were used as precursors to generate high loadings of metal sites finely dispersed on SBA-15 silica. To achieve this, grafting of chelated transition metal precursors was performed directly to the surface of the as-synthesized SBA-15/P123 composite material. The thus-obtained metal/SBA-15 materials were studied by a variety of methods, e.g., elemental analysis, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance UV-visible spectroscopy (DR-UV-vis), X-ray photoelectron spectroscopy (XPS) and N2 physisorption measurements at -196 °C. From the results, the proposed functionalization method was found to be a highly tunable and reproducible strategy to disperse transition metal oxides in mesoporous silica materials. The results from elemental analysis of the modified materials confirmed that the amount of grafted species is a function of the initial concentration of precursor in the solution used for grafting. The chelated complexes were found to strongly interact with the silanol groups of the silica material, resulting in a ligand-exchange process, as corroborated by FTIR. However, different metal precursors showed distinct reactivity towards the surface of mesoporous silica, owing to differences in the stability of the complexes under the conditions used for grafting. DR-UV-vis and XPS analyses suggest that when the stability of a given precursor decreases, the grafting procedure can lead to the formation of small clusters of the metal oxide on the silica surface. XRD and SEM also show that grafting of lower stability complexes, such as Mn(acac)3, Cu(acetate)2 and VO(acac)2, on the silica surface can result in the formation of large crystals on the external surface of the SBA-15 particles. Nevertheless, it was established by XPS analysis that only a small percentage of the grafted species leads to the formation of bulk crystals while the remaining species are substituted into the silica framework. Obviously, a well-controlled and increased dispersion of the metal cations/oxides on the surface of highly porous silica materials is of great interest since these M(x)O(y)-SiO2 mixed oxides could demonstrate high catalytic activity in a large variety of reactions.
authors.affiliation: Department of Chemistry, Université Laval, Quebec G1V 0A6, QC, Canada; Department of Chemical Engineering, Université Laval, Quebec G1V 0A6, QC, Canada.
authors.forename: François
authors.initials: F
authors.lastname: Bérubé
authors.affiliation: Department of Chemistry, Université Laval, Quebec G1V 0A6, QC, Canada.
authors.forename: Abdelkarim
authors.initials: A
authors.lastname: Khadraoui
authors.affiliation: Department of Chemistry, Université Laval, Quebec G1V 0A6, QC, Canada; Centre de Recherche sur les Matériaux Avancés (CERMA), Université Laval, Quebec, QC, Canada.
authors.forename: Justyna
authors.initials: J
authors.lastname: Florek
authors.affiliation: Department of Chemical Engineering, Université Laval, Quebec G1V 0A6, QC, Canada.
authors.forename: Serge
authors.initials: S
authors.lastname: Kaliaguine
authors.affiliation: Department of Chemistry, Université Laval, Quebec G1V 0A6, QC, Canada; Centre de Recherche sur les Matériaux Avancés (CERMA), Université Laval, Quebec, QC, Canada. Electronic address: freddy.kleitz@chm.ulaval.ca.
authors.forename: Freddy
authors.initials: F
authors.lastname: Kleitz
keywords: Chelates; Grafting; Mesoporous hybrids; Pore surface; SBA-15; Solid catalysts; Transition metals