Nanoparticles of Fe 2O 3 inserted in SBA-15 silica at micropore mouth level: An experimental evidence of the confinement effect

Abstract

Nanometric Fe 2O 3 particles could be inserted inside the internal pore volume of SBA-15 mesoporous silica when Fe(III) chelates (EDTA, gluconate and citrate) were used as impregnating precursors. Fe(III) nitrate preferentially yields 8 nm uniformly sized Fe 2O 3 clusters that selectively plug the SBA-15 channels through a geometric confinement effect. An oxidative degradation of Fe-chelate precursors yielded Fe(III) oxidic particles of various sizes and dispersion, depending on the nature and geometry of chelate anion. Fe(EDTA) precursors specifically generated Fe 2O 3 nanoparticles that selectively migrate towards two types of positions where the silica surface exhibits a high curvature. In samples involving low Fe loadings, Fe 2O 3 particles first creep towards the silica micropore mouths (nests), in which they are readily confined and stabilized. For higher Fe loadings, when most of the micropore nests were filled, oxidic particles eventually settle as a superficial film on the mesopore walls and undergo stabilization onto the surface roughness that can also favors their confinement, as theoretically predicted by Derouane and co-workers. Upon further reduction, as selectively followed by combined cyclic voltammetry and TPR, Fe 2O 3 readily yield FeO nanoslabs that remain even more efficiently confined within their respective nest positions through a further acid–base type stabilization.