Zirconium oxide nanoparticles coated on sepiolite by sol–gel process — Their application as a solvent-free catalyst for condensation reactions

An inorganic nanocomposite made of zirconia nanoparticles coated on the external surfaces of the fibrous clay mineral sepiolite was prepared by using the sol–gel process under soft conditions using zirconium(IV) propoxide in 1-propanol as the precursor. The resulting materials were characterized by X-ray diffraction (XRD), thermal gravimetric analyses (TGA) and differential thermal analyses (DTA), microporosimetry, 29Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR), and high-resolution transmission electron microscopy (HR-TEM). The organic material from the precursor was fully removed after calcination at 450 °C, concurrently with the crystallization of the cubic phase of zirconium oxide. The coordinated water molecules of sepiolite were fully removed and its symmetrical layered structure was folded after calcination at 650 °C, as observed by XRD and 29Si cross-polarization (CP) / MAS NMR. The arrangement of the nanoparticles of zirconium oxide on the sepiolite external surfaces maintains a fibrous morphology for the nanocomposite. This material was applied as a catalyst for the Knoevenagel condensation reaction of benzaldehyde and malononitrile under solvent-free conditions. Strongly improved yields of reaction, attributed to larger catalytically active surfaces, were obtained compared with either the sepiolite clay mineral or the zirconium oxide tested individually.