Theoretical and Experimental Study for Cross-Coupling Aldol Condensation over Mono- and Bimetallic UiO-66 Nanocatalysts.

Mono- and bimetallic UiO-66 nanocatalysts were synthesized using the solvothermal synthesis method and evaluated in the aldol condensation reaction of benzaldehyde and acetone in a batch reactor. N₂ physisorption, thermogravimetric analysis, temperature-programmed desorption of ammonia, X-ray diffraction, field-emission scanning electron microscopy–energy-dispersive X-ray, X-ray photoelectron spectroscopy, potentiometric titration, and Fourier transform infrared were used to characterize the nanocatalysts. The higher activity exhibited by the Zr/Hf-UiO-66 catalyst could be attributed to the lower orbital energy interaction with benzaldehyde, as shown by density functional theory. A synergetic effect is observed for the bimetallic UiO-66 nanocatalyst between Zr and Hf, obtaining a higher reaction rate than the monometallic nanocatalysts. Meanwhile, this antagonistic effect was shown in the bimetallic catalysts between Zr and Ce, which was less active than the monometallic UiO-66 catalyst due to free COOH generated during the synthesis. Finally, the selectivity results showed that incorporating Hf and Ce on Zr-UiO-66 favors benzalacetone formation by cross-coupling condensation of benzaldehyde and acetone at isoconversion conditions. [ABSTRACT FROM AUTHOR]