Pazo-Carballo, C., Camu, E., Hidalgo-Rosa, Y., Llanos, J., Zárate, X., Dongil, A. B., Schott, E. & Escalona, N. (2025). Selective Benzaldehyde/Acetone to benzalacetone Cross-Aldol Condensation Catalyzed by UiO-66 MOFs. Dalton Transactions. https://doi.org/10.1039/D5DT00494B

Abstract: Cross-aldol condensation reactions are an important family of reactions that generate added-value chemicals with long chain products. Those products have multiple applications, such as those in the pharmaceutical industry, flavors and fragrances, agricultural chemicals and fine and specialty chemicals, among others. Possible products are long chain aromatic compounds, which could be used to generate fuels. The ability to generate that kind of fuel from biomass has been a challenge over the last few years. In this report the cross-aldol condensation reaction study using a family of UiO-66 MOFs between benzaldehyde and acetone to produce benzalacetone was performed. Thus, a family of UiO-66 MOFs was synthesized and characterized (by means of N₂ physisorption, NH₃-TPD, CO₂-TPD, ATR-FTIR, and powder X-ray diffraction) and its catalytic activity was studied in detail. Good conversion and selectivity were obtained. A thorough study of the kinetics of this reaction was performed for all the used UiO-66 MOFs. In this sense, the Langmuir–Hinshelwood kinetic models fitted the experimental data. The behavior predictions using different metals (Zr, Hf or Zr/Hf) and linkers (BDC or PDC) were fitted from the bimolecular one-site and two-site models. Competitive and non-competitive mechanisms were used to explain the production of the main intermediate compound (β-hydroxy ketone). The catalyst Zr/Hf-UiO-66 showed the best activity, which could be attributed to the greater total interaction energy of benzaldehyde/acetone on the catalyst surface (as shown by DFT calculations). A synergetic effect is observed for the bimetallic UiO-66 catalyst between Zr and Hf, obtaining a higher reaction rate than for the monometallic catalysts. Furthermore, a similar effect was reflected in the TOF for Zr/Hf-UiO-66. The best selectivity towards benzalacetone was obtained for Hf-UiO-66-PDC under iso-conversion conditions. Finally, depending on the metal–linker pair, differences in the benzaldehyde/acetone adsorption modes were observed, indicating the presence of bimolecular kinetic adjustments at one and two sites for the aldol condensation of benzaldehyde. All the results shown herein were supported by means of DFT calculations.