The catalytic activity of Mg-Al hydrotalcite (HT) materials in base-catalyzed reactions is known to be promoted by the low crystallinity of the HT solid. In the present work, two routes enabling the preparation of finely crystalline Mg-Al HT materials were explored: (1) the inverse microemulsion technique, and (2) co-precipitation in the presence of starch. Carbonate, chloride and bromide forms of HT were prepared, examined with X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy and infrared spectroscopy, and used as catalysts in the Baeyer–Villiger oxidation of cyclohexanone to ε-caprolactone with a H2O2/acetonitrile system. The bromide forms proved significantly less active than the chlorides and carbonates, as they promoted nonselective consumption of H2O2. The fine crystalline materials were more active than the more crystalline HT references obtained by conventional co-precipitation. Catalysts prepared by inverse microemulsion were less crystalline and more active than the starch-templated ones, but suffered stronger deactivation by the acidic reaction environment. Alkalization of the reaction medium with NaHCO3 stabilized the HT materials and increased the ε-caprolactone yield, which became comparable for both types of fine crystalline catalysts—thus pointing to the synthesis involving a simple and cheap starch templating approach as being a particularly attractive one.
Fine Crystalline Mg-Al Hydrotalcites as Catalysts for Baeyer-Villiger Oxidation of Cyclohexanone with H2O2