A monolithic composite based on zeolite-like metal-organic framework@divinylbenzene polymer separates azeotropic fluorocarbon mixture efficiently

•Organic monolithic columns are still less common in Gas chromatography.•ZMOFs incorporation expands monolithic columns’ capabilities to separate small molecules.•ZMOF@DVB monolithic composite allows performing conventional low-pressure GC separations.•ZMOF brings a nonpolar character to the monolithic material enhancing its separation ability toward hydrocarbons.•ZMOF@DVB monolithic composite efficiently separates R-410A fluorocarbon azeotropic mixture.•The composite stationary phase brings the advantages of its component materials together. Organic monolithic columns are mainly used to separate macromolecules; however, many attempts to extend their performance toward small molecules were examined by incorporating micro- and nanoparticles. The incorporation technique enabled utilizing organic monoliths in gas chromatography (GC) for small molecules, which are still scarce. Here, we prepared a composite matrix of capillary monolithic columns of a zeolite-like metal-organic framework with a sodalite topology (sod-ZMOF) and Divinylbenzene polymer (DVB) for GC separations under 0.5 MPa. Relatively short DVB monolithic columns (18 cm long × 0.25 mm i.d.) incorporated with a tiny amount of sod-ZMOF nanoparticles (0.7 and 1.17 wt%) with an average particle size of 225 nm were successfully fabricated and used to separate linear alkanes and polar probes mixtures with increasing resolution up to 3.7 and 5.1 times, respectively, compared to a blank DVB monolithic column. A high-performance separation of linear alkanes series mixture (methane to decane) was exhibited in less than 2 min. McReynolds constants revealed that sod-ZMOF provided the composite monolith with a nonpolar character yielding a negative average polarity value smaller than the standard squalene column. An Excellent retention time of pentane and octane day-to-day reproducibility was achieved during 16 days and over more than 500 runs with RSD% of 2.25% and 3.3% using a composite monolithic column with 5 mg mL−1 sod-ZMOF (5-ZMOF@DVB). In addition, a qualitative determination of the gas mixture content of three commercially available Lighter gas cartridges was performed via the 5-ZMOF@DVB column. Finally, successfully separating an azeotropic freon mixture of difluoromethane (R-32) and pentafluoroethane (R-125) was achieved with a selectivity of up to 4.84. A further thermodynamic study related the preferential adsorption of R-125 to entropic factors rather than enthalpic while trapping inside ZMOF po