Lanthanide metal–organic
frameworks (Ln-MOFs) have attracted
considerable interest in heterogeneous catalysis due to their tunable
channel sizes, stable network structures, and diverse active sites.
Here, a series of lanthanum (La)-based MOFs were synthesized in the
presence of various amine modulators of ethylene diamine (ED), 1,4-diazabicyclo[2.2.2]octane
(DABCO), butylamine (BA), triethylamine (TEA), and heptylamine (HA)
under identical conditions. These modulators play a crucial role in
both the nucleation and growth processes of the La-MOFs. The impact
of these modulators on crystallinity, porosity, acidity, thermal stability,
bonding, morphology, and oxidation state of the metal was investigated.
Textural analysis confirmed that the MOFs possess identical crystalline
structures but different morphologies. The catalytic performance of
the as-prepared La-MOF catalysts was evaluated for levulinic acid
(LA) esterification. La-MOF-DABCO exhibited the highest yield, producing
92% ethyl levulinate (EL) in 2 h at 190 °C. Kinetic parameters
indicated an activation energy of 20.7 kJ mol–1 and
a reaction order of 0.5 with respect to LA. Thermodynamic analysis
classified the reaction as endergonic, nonspontaneous, and more ordered.
The study illuminated the influence of Brønsted–Lewis
acid sites of La-MOF on catalytic esterification, highlighting a modulator-driven
approach to MOF synthesis and its potential in heterogeneous catalysis.
These findings offer insights for modeling and simulation studies
in industrial applications.