Alkyl modified cationic COFs for preferential trapping of charge dispersed perrhenate: Synergistic hydrophobicity and anion-recognition effects.

Charge dispersed oxoanionic pollutants (such as TcO4- and ReO4-) with low hydrophilicity are typically difficult to be preferentially extracted. Recently, cationic covalent organic frameworks (COFs) have received considerable attention for anions trapping. Two cationic COFs, denoted as Tp-S and Tp-D, were synthesized by incorporating ethyl and cyclic alkylated diquats into 2,2'-bipyridine-based COF. A synergistic effect of hydrophobic channel and anion-recognition sites were achieved by branched chains, which effectively surmounted the Hofmeister bias. Both Tp-S and Tp-D exhibited raising removal performance for surrogate ReO4- at high acidity with adsorption capacities of 435.6 and 291.4 mg g-1, respectively. Obvious variations caused by side chains were displayed in microstructures and adsorption performance. Specially, compared with Tp-D, Tp-S demonstrated desirable priority in uptake capacity and selectivity. In a real-scenario experiment, Tp-S could remove 72.8 % of ReO4- in a simulated Hanford LAW stream, which was attributed to the spatial effects and charge distribution arising from the open and flexible side chains of Tp-S. Otherwise, the rigid cyclic chains endowed pyridine-base Tp-D material an unprecedented alkaline stability. Spectra and theoretical calculations revealed a mechanism of preferential capture based on electrostatic interaction and hydrogen bonding between charge dispersed ReO4-/TcO4- and Tp-S/Tp-D. This work provides an innovative perspective to tailored materials for the treatment of oxoanionic contaminants.

Chelating effect between uranyl and pyridine N containing covalent organic frameworks: A combined experimental and DFT approach.

Covalent organic frameworks (COFs) are promising adsorbents for removing heavy metal ions, and have high crystallinity, a porous structure, and conjugated stability. N-containing functional groups are known to have great affinity for uranyl ions. In this work, to explore the peculiarity of the pyridine N structure as an efficient adsorbent, we chose 2,2'-dipyridine-5,5'-diamine (Bpy) and pyridine-2,5'-diamine (Py) as the core skeletons, and 1,3,5-triformylphloroglucinol (Tp) as the linker to synthesize two crystalline and stable N-containing COFs named TpBpy and TpPy, respectively, through a facile solvothermal method. Characterization results demonstrated that TpBpy and TpPy possessed regularly growing pore sizes, large specific surface areas and relatively strong thermal resistances. The results of batch experiments showed that both COF materials were capable of the effective removal of uranyl with uptake capacities of 115.45 mg g-1 and 291.79 mg g-1, respectively. In addition, density functional theory (DFT) simulations highlighted the beneficial chelation effect of the double N structure in pyridine monomers for removing uranyl ions. Combining systematic experimental and theoretical analyses, the adsorption process and interaction mode of porous COFs and UO22+ were revealed, to provide predictable support for the application of pyridine N-containing COFs in the field of environmental remediation.

Efficient elimination of Cr(VI) from aqueous solutions using sodium dodecyl sulfate intercalated molybdenum disulfide.

In recent years, the heavy metal ions have been immoderately released into the ecological system and result in potential hazardous to public health. Herein, the sodium dodecyl sulfate intercalated molybdenum disulfide (SDS-MoS2) was synthesized for the adsorption of Cr(VI). The SDS molecule was flat and vertically intercalated into the interlayer of MoS2, which was further evidenced by density functional theory calculations. The capture of Cr(VI) on the sphere-like SDS-MoS2 relied on solution pH. The retention of Cr(VI) on SDS-MoS2 attained 63.92 mg/g, and the removal process was endothermic, spontaneous and increased with temperature increasing. The main removal mechanism of Cr(VI) onto SDS-MoS2 was Cr(VI) fixing on the surface of the composites by chemisorption involving possible Cr-S coordination bonding. More importantly, Cr(VI) passed into the increased interlamination and reacted at the interlamination of SDS-MoS2, which was further proved at molecular level. The results can provide critical information for the application of SDS-MoS2 in Cr(VI) elimination or other kinds of pollutants removal in natural aquatic environment.