Bifunctional adsorbents based on hyper-cross-linked polymers containing carbonyl and amine species for the efficient removal of diclofenac from water in a broad pH range

Development of new adsorbents for the efficient removal of organic pollutants from water is one of the most emerging environmental issues. Current studies in this field focus on improving the adsorption capacity of various materials and/or broadening the pH range in which the adsorbents can efficiently remove target pollutants. In this study, we designed bifunctional hyper-cross-linked polymers (HCPs) containing both carbonyl and amine species to investigate the effect of amine functional groups on the efficiency of adsorptive removal of non-steroidal anti-inflammatory drugs (NSAIDs) from water. We revealed that post-synthesis functionalization of carbonyl-rich HCPs with amine species does not have a significant impact on the adsorption capacity of these polymers under strongly acidic conditions (pH < 4; q_e ∼ 544 mg/g), but significantly extends the pH range in which bifunctional polymers can adsorb diclofenac. For example, at native pH (pH ∼ 6), bifunctional HCP-based adsorbents exhibited an adsorption capacity approximately 8 times higher than that of pristine materials (q_e = 191 vs. 24 mg/g, respectively). Furthermore, it was revealed that the adsorbents designed in this study can efficiently remove diclofenac from complex water matrices and exhibit high stability in several adsorption-desorption cycles. Moreover, we demonstrated that selecting a cross-linker with a longer chain results in a polymer with a lower surface area and smaller average pore size, while enabling higher efficiency in amine incorporation via post-synthesis functionalization. This latter feature was crucial for ensuring the high adsorption capacity of HCP-based adsorbents in the removal of NSAID at neutral pH.