Unveiling the Impact of Diverse Morphology of Ionic Porous Organic Polymers with Mechanistic Insight on the Ultrafast and Selective Removal of Toxic Pollutants from Water

Abstract

In recent years, detoxification of contaminated water by different types of materials has received a great deal of attention. However, lack of methodical in-depth understanding of the role of various physical properties of such materials toward improved sorption performance limits their applicable efficiencies. In perspective, decontamination of oxoanion-polluted water by porous materials with different morphologies are unexplored due to a shortfall of proper synthetic strategies. Herein, systematic optimization of sequestration performance toward efficient decontamination of toxic oxoanion-polluted water has been demonstrated by varying the morphologies of an imidazolium-based cationic polymeric network [ionic porous organic polymers (iPOP-5)]. Detailed morphological evolution showed that the chemically stable ionic polymer exhibited several morphologies such as spherical, nanotube, and flakes. Among them, the flakelike material [iPOP-5(F)] showed ultrafast capture efficiency (up to ∼99 and >85% removal within less than 1 min) with high saturation capacities (301 and 610 mg g–1) toward chromate [Cr(VI)] and perrhenate [Re(VII)] oxoanions, respectively, in water. On the other hand, the spherical-shaped polymer [iPOP-5(S)] exhibited relatively slow removal kinetics (>5 min for complete removal) toward both Cr(VI) and Re(VII) oxoanions. Notably, iPOP-5(F) eliminated Cr(VI) and Re(VII) selectively even in the presence of excessive (∼100-fold) competing anions from both high- and low-concentration contaminated water. Further, the compound demonstrated efficient separation of those oxoanions in a wide pH range as well as in various water systems (such as potable, lake, river, sea, and tannery water) with superior regeneration ability. Moreover, as a proof of concept, a column exchange-based water treatment experiment by iPOP-5(F) has been performed to reduce the concentration of Cr(VI) and Re(VII) below the WHO permitted level. Mechanistic investigation suggested that the rare in situ exfoliation of flakes into thin nanosheets helps to achieve ultrafast capture efficiency. In addition, detailed theoretical binding energy calculations were executed in order to understand such rapid, selective binding of chromate and perrhenate oxoanions with iPOP-5(F) over other nonmetal-based anions.