In this work, the inclusion of free sulfonic acid groups in highly stable MOFs is explored. The synthesized catalysts have been applied in a model esterification reaction. Two metal organic frameworks bearing sulfonic acid moieties are investigated: HSO₃-MIL-101(Cr) synthesized following different approaches and a new structure based on HSO₃-bdc and Zr. The acidic properties, catalytic performance, deactivation and stability of the different structures are critically evaluated. In the case of MIL-101(Cr), deactivation of the sulfonic groups via formation of butanol sulfonic esters has been observed. Due to the strong interaction between –SO₃ ⁻ and the Cr open metal site where usually fluorine (F⁻) is located in the structure, the HSO₃-MIL-101(Cr) catalysts are not stable under acidic regeneration conditions. When using Zr as a metal node, a new and stable sulfonic acid containing porous structure was synthesized. This structure showed high activity and full re-usability in the esterification of n-butanol with acetic acid. In this case, deactivation of the catalyst due to sulfonic ester formation could be reversed by reactivation under acidic conditions.

Four metal-organic frameworks (MOFs), specifically UiO-66, UiO-66-NH₂, UiO-66-NO₂, and MIL-53(Al), were synthesized, characterized, and used as sorbents in a dispersive micro-solid phase extraction (D-µSPE) method for the determination of nine pollutants of different nature, including drugs, phenols, polycyclic aromatic hydrocarbons, and personal care products in environmental waters. The D-µSPE method, using these MOFs as sorbents and in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD), was optimized. The optimization study pointed out to UiO-66-NO₂ as the best MOF to use in the multi-component determination. Furthermore, the utilization of isoreticular MOFs based on UiO-66 with the same topology but different functional groups, and MIL-53(Al) to compare with, allowed us for the first time to evaluate the influence of such functionalization of the ligand with regards to the efficiency of the D-µSPE-HPLC-DAD method. Optimum conditions included: 20 mg of UiO-66-NO₂ MOF in 20 mL of the aqueous sample, 3 min of agitation by vortex and 5 min of centrifugation, followed by the use of only 500 µL of acetonitrile as desorption solvent (once the MOF containing analytes was separated), 5 min of vortex and 5 min of centrifugation. The validation of the D-µSPE-HPLC-DAD method showed limits of detection down to 1.5 ng·L⁻¹, average relative recoveries of 107% for a spiked level of 1.50 µg·L⁻¹, and inter-day precision values with relative standard deviations lower than 14%, for the group of pollutants considered.