Revisiting molecular adsorption: unconventional uptake of polymer chains from solution into sub-nanoporous media

Adsorption of polymers from the solution phase has been extensively studied to cope with many demands not only for separation technologies, but also for the development of coatings, adhesives, and biocompatible materials. Most studies hitherto focus on adsorption on flat surfaces and mesoporous adsorbents with open frameworks, plausibly because of the preconceived notion that it is unlikely for polymers to enter a pore with a diameter that is smaller than the gyration diameter of the polymer in solution; therefore, sub-nanoporous materials are rarely considered as a polymer adsorption medium. Here we report that polyethylene glycols (PEGs) are adsorbed into sub-nanometer one-dimensional (1D) pores of metal-organic frameworks (MOFs) from various solvents. Isothermal adsorption experiments reveal a unique solvent dependence, which is explained by the balance between polymer solvation propensity for each solvent and enthalpic contributions that compensate for potential entropic losses from uncoiling upon pore admission. In addition, adsorption kinetics identify a peculiar molecular weight (MW) dependence. While short PEGs are adsorbed faster than long ones in single-component adsorption experiments, the opposite trend was observed in double-component competitive experiments. A two-step insertion process consisting of (1) an enthalpy-driven recognition step followed by (2) diffusion regulated infiltration in the restricted 1D channels explains the intriguing selectivity of polymer uptake. Furthermore, liquid chromatography using the MOFs as the stationary phase resulted in significant PEG retention that depends on the MW and temperature. This study provides further insights into the mechanism and thermodynamics behind the present polymer adsorption system, rendering it as a promising method for polymer analysis and separation.