Synthetic Mg-Al hydrotalcites (HT) are environmentally friendly solid bases frequently applied as catalysts in base catalyzed reactions. The most common synthesis method, using NaOH as precipitant, is problematized by the possibility of introducing undesired Na contamination. Alkali-free synthesis is usually performed with NH3aq, a precipitant which is less efficient in incorporation of Mg into HT lattice. In the present work, organic bases, tetrabutylammonium hydroxide and choline hydroxide, were successfully employed as precipitating agents in a new alkali-free route of Mg-Al HT synthesis. HT solids were also obtained with inorganic bases, NH3aq and NaOH. Characterization with X-ray diffraction, elemental analysis, scanning electron microscopy, Fourier-transform infrared spectroscopy and thermogravimetry/differential scanning calorimetry, confirmed the formation of nanocrystalline HT compounds with all employed bases. HT prepared with NH3aq exhibited an Mg deficit, which was detrimental to the catalytic activity in base catalyzed reactions. The effect was attributed to the tendency of Mg2+ to form ammine complexes, a conclusion supported by quantum mechanical calculations. HT prepared with NaOH showed the highest crystallinity, which was unfavorable for catalytic application. The addition of starch to the synthesis medium provided a means by which to diminish the crystal size of all HT precipitates. Catalytic tests of the Baeyer-Villiger oxidation of cyclohexanone demonstrated that the highest yields of ε-caprolactone were obtained with fine-crystalline HT catalysts prepared with organic bases in the presence of a starch template.
Keywords: Baeyer–Villiger oxidation; alkali-free synthesis; biotemplate; choline hydroxide; crystallinity; hydrotalcite; organic base; starch; tetrabutylammonium hydroxide.