The Al-Containing Silicates Modified with Organic Ligands and SnO₂ Nanoparticles for Catalytic Baeyer-Villiger Oxidation and Aerobic Carboxylation of Carbonyl Compounds

The Baeyer-Villiger Oxidation (BVO) of ketones and aldehydes produce lactones and formates, while aerobic carboxylation of aldehydes manufactures carboxylic acids, both having high added value. This work prepared a series of Al-containing silicates modified with organic ligands and SnO₂ nanoparticles, which were then employed as catalyst in BVO and carboxylation. Characterizations revealed the morphology of the synthesized catalyst was changed from micron-sized thin sheets to smaller blocks, and then to uniform nanoparticles (size of 50 nm) having the doped SnO₂ nanoparticles with a size of 29 nm. All catalysts showed high BET surface areas featuring silt-like mesopores. In determining the priority of BVO and carboxylation, an influence evaluation of the parameters showed the order to be substrate > oxidant > solvent > catalyst. Cyclic aliphatic ketones were suitable for BVO, but linear aliphatic and aromatic aldehydes for carboxylation. Coordination of (<i>S</i>)-binaphthol or doping of Sn into catalyst showed little influence on BVO under <i>m</i>-CPBA, but the Sn-doped catalyst largely increased BVO under (NH₄)₂S₂O₈ and H₂O₂. Calculations revealed that the catalyst containing both Al and Sn could give BVO intermediates lower energies than the Sn-beta zeolite model. The present system exhibited merits including wider substrate scope, innocuous catalytic metal, greener oxidant, as well as lower catalyst cost.