Satyam Saurabh

Multiple functional groups decorated ionic macroporous metal–organic framework (MOF) for large-scale, selective uranium recovery from unspiked natural seawater.

) from the mixture of excessive (∼1000-fold) other interfering anions to well below the permissible drinking water limit. Moreover, the hybrid cationic nanotrap material can reduce the As(V) level from a highly contaminated groundwater sample to below the WHO permitted level.

Abstract On‐demand uranium extraction from seawater (UES) can mitigate growing sustainable energy needs, while high salinity and low concentration hinder its recovery. A novel anionic metal‐organic framework (iMOF‐1A) is demonstrated adorned with rare Lewis basic pyrazinic sites as uranyl‐specific nanotrap serving as robust ion exchange material for selective uranium extraction, rendering its intrinsic ionic characteristics to minimize leaching. Ionic adsorbents sequestrate 99.8% of the uranium in 120 mins (from 20,000 ppb to 24 ppb) and adsorb large amounts of 1336.8 mg g −1 and 625.6 mg g −1 from uranium‐spiked deionized water and artificial seawater, respectively, with high distribution coefficient, K d U ≥ 0.97 × 10 6 mL g −1 . The material offers a very high enrichment index of ≈5754 and it achieves the UES standard of 6.0 mg g −1 in 16 days, and harvests 9.42 mg g −1 in 30 days from natural seawater. Isothermal titration calorimetry (ITC) studies quantify thermodynamic parameters, previously uncharted in uranium sorption experiments. Infrared nearfield nanospectroscopy (nano‐FTIR) and tip‐force microscopy (TFM) enable chemical and mechanical elucidation of host‐guest interaction at atomic level in sub‐micron crystals revealing extant capture events throughout the crystal rather than surface solely. Comprehensive experimentally guided computational studies reveal ultrahigh‐selectivity for uranium from seawater, marking mechanistic insight.

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.

Abstract Metal‐based oxoanions are potentially toxic pollutants that can cause serious water pollution. Therefore, the segregation of such species has recently received significant research attention. Even though several adsorbents have been employed for effective management of chemicals, their limited microporous nature along with non‐monolithic applicability has thwarted their large‐scale real‐time application. Herein, we developed a unique anion exchangeable hybrid composite aerogel material (IPcomp‐6), integrating a stable cationic metal–organic polyhedron with a hierarchically porous metal–organic gel. The composite scavenger demonstrated a highly selective and very fast segregation efficiency for various hazardous oxoanions such as, HAsO 4 2− , SeO 4 2− , ReO 4 − , CrO 4 2− , MnO 4 − , in water, in the presence of 100‐fold excess of other coexisting anions. The material was able to selectively eliminate trace HAsO 4 2− even at low concentration to well below the As V limit in drinking water defined by WHO.