Safaei, S.,
Tangestaninejad, S.,
Moghadam, M.,
Bahadori, M.,
Mohammadpoor baltork, I.,
Omidvar, A.,
Mirzaeian, M. Journal of Industrial and Engineering Chemistry (1226086X)
Herein, vanadyl acetylacetonate and manganese(Ⅱ) acetylacetonate complexes were anchored into aminated UiO-66(Zr) via a condensation reaction (V-SB-UiO-66 and Mn-SB-UiO-66), where terminal amine groups formed imine linkage with the metal acetylacetonate complexes. Unlike conventional post-synthetic modification (PSM) strategies, our approach eliminates complex ligand exchange processes, offering a versatile platform for designing robust heterogeneous catalysts. This PSM approach, utilizing straightforward linker functionalization, introduces catalytic sites onto the MOF structure, facilitating heterogeneous catalytic epoxidation reactions. Comprehensive characterization techniques, including PXRD, N2 adsorption/desorption, FT-IR, FE-SEM, ICP-OES, TG-DTG, and XPS, confirmed the structural integrity during the PSM, successful anchoring of acetylacetonate complexes, the catalyst surface constitution and location of active Schiff-base functionalities on the UiO-66 scaffold. The density functional theory (DFT) calculations are also performed to investigate the pristine as well as functionalized MOFs. The structural and electronic properties, binding energies, reactivity descriptors, and time-dependent DFT (TD-DFT) analyses are performed to determine the behaviour of the considered systems. The catalytic performance of these Schiff base-functionalized UiO-66 s was evaluated for olefin epoxidation by tert-butyl hydroperoxide (TBHP) under various reaction conditions, achieving 44–99 % conversion and 57–96 % selectivity for cyclic, linear, and aromatic alkenes. Additionally, these catalysts demonstrated reusability for up to five cycles without significant structural changes. © 2025
