Preparation of value-added metal-organic frameworks for high-performance liquid chromatography. Towards green chromatographic columns

This work applies the concepts of green chemistry, where polyethylene terephthalate (PET) bottles were used as the acid-dicarboxylic linker source for the synthesis of MIL-53(Al) metal organic frameworks (MOFs) and then used as a stationary phase for the separation of various solutes and compared with MIL-53(Al) synthesized from traditional terephthalic acid. Both synthesized MIL-53(Al) MOFs were characterized by scanning electron microscopy (SEM), FT-IR, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and specific surface area analysis. Eight groups of standard analytes in addition to real samples were tested to evaluate the separation performance of the MIL-53(Al) packed columns in HPLC under various chromatographic conditions. Based on elution order of the studied compounds and the effects of mobile phase composition, the working mechanism was reversed phase mode in the presence of size-exclusion effects for large molecules, which exceeded the dynamic diameter of MIL-53(Al) (similar to 7.6 angstrom). The effects of stationary phase sieving, mobile phase flow rate and composition, injected sample mass, and temperature were investigated relative to the chromatographic behavior of MIL-53(Al). MIL-53(Al) particle sieving before packing reduced peak broadening and significantly enhanced the chromatographic performance of the prepared columns up to 2.26 times relative to the number of theoretical plates. The MIL-53(Al) packed columns offered high-resolution separation for all studied mixtures with R-s >2 and good stability and long-term durability. At optimal conditions, the prepared columns exhibited efficiencies between 5600-63200 plates m(-1). Higher efficiencies were observed for alkylbenzenes and polyaromatic hydrocarbons as the organic linker in the MIL-53(Al) structure, which improved retention and separation of aromatics through pi-pi interactions. Thermodynamic parameters including Delta H, Delta S, and Delta G for the transfer of analyte from the mobile phase to the MIL-53(Al) stationary phase were studied. Compared with previously cited MOFs packed columns, the present MIL-53(Al) columns gave comparable selectivity and much better efficiency for most of the studied chemicals at optimum conditions, indicating the feasibility of MIL-53(Al) as a stationary phase for HPLC applications. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

This study utilized PET bottles to synthesize MIL-53(Al) MOFs as stationary phases for HPLC, demonstrating high-resolution separation performance for various solutes.