Abstract
This study delves into the thermodynamics of liquid-phase adsorption on hypercrosslinked polystyrene networks (HPSNs), widely recognized for their distinct structure and properties. Despite the considerable progress in HPSN synthesis and characterization, gaps persist regarding the chromatographic retention mechanism, thermodynamics of adsorption, and their impact on the adsorption selectivity, especially in the case of networks with ultra-high crosslinking densities (up to 500%). Utilizing high-performance liquid chromatography (HPLC), we have explored, for the first time, the thermodynamic intricacies of liquid-phase adsorption onto HPSNs crosslinked in the entire range of the crosslinking degree from 100 to 500%. Our findings reveal the dependences of thermodynamic characteristics and selectivity of adsorption on the crosslinking degree, textural features, and liquid-phase composition in the region of extremely low adsorbent surface coverages (Henry's range). We have detected that, in the case of HPSNs, the dependence of the thermodynamic characteristics of adsorption on the liquid-phase composition is different than for classical HPLC stationary phases. Moreover, we scrutinize the impact of the molecular structure of the studied aromatic compounds on the thermodynamic characteristics and selectivity of the liquid-phase adsorption on HPSNs. Investigating liquid-phase adsorption selectivity, we demonstrate the pivotal role of π-π interactions in separating aromatic compounds on HPSNs. Eventually, we unveil that the thermodynamic characteristics of adsorption peculiarly depend on the crosslinking degree due to the profound impact of the crosslinking on the electronic density in benzene rings in HPSNs, whereas the separation throughput peaks for the polymer with a 500% crosslinking degree, attributed to its exceptionally rigid network structure, moderate swelling and micropore volume, and minimum specific surface area.