Solvent-free cross aldol condensation of aldehydes and ketones over SrMo1-xNixO3-δ perovskite nanocrystals as heterogeneous catalysts

Abstract

Aldol condensation is arguably one of the most fascinating reactions that leads to the formation of C–C bonds. Its use in the pharmaceutical industry to synthesis complex drugs from simple aldehydes and ketones has become of paramount importance. Although this is one reaction that has lured a lot of attention, not enough has been explored in heterogeneous catalysis. In this work we have successfully synthesized multicationic perovskites via the soft-template method and characterized them thoroughly. The synthesized perovskite nanocrystals were found to have small SBET however their catalytic application in the conversion of benzaldehyde (BAL) in the aldol condensation with diethyl ketone (DEK) was found to be astonishing. The synthesis was confirmed using many techniques, from determining the oxidation states of the materials using XPS. This gave access to determine the coordination of the metals in the perovskite lattice and also qualitatively assess the oxygen environments that exist. The oxygen vacancies and SBET were used to assess the activity of the perovskite catalysts in the cross-aldol condensation reaction. The optimal conditions for this aldol condensation were found to be 120 °C after 25 h with no solvent using SrMo0.5Ni0.5O3-δ inorganic perovskite which had the highest amount of oxygen vacant sites which gave a conversion of 88 % and an 82 % selectivity towards the desired cross-aldol condensation product. The use of dimethylformamide (DMF) for this reaction is discouraged as it reacts with BAL to produce a higher amide.