Twistedly hydrophobic basis with suitable aromatic metrics in covalent organic networks govern micropollutant decontamination.

The pre-designable structure and unique architectures of covalent organic frameworks (COFs) render them attractive as active and porous medium for water crisis. However, the effect of functional basis with different metrics on the regulation of interfacial behavior in advanced oxidation decontamination remains a significant challenge. In this study, we pre-design and fabricate different molecular interfaces by creating ordered π skeletons, incorporating different pore sizes, and engineering hydrophilic or hydrophobic channels. These synergically break through the adsorption energy barrier and promote inner-surface renewal, achieving a high removal rate for typical antibiotic contaminants (like levofloxacin) by BTT-DATP-COF, compared with BTT-DADP-COF and BTT-DAB-COF. The experimental and theoretical calculations reveal that such functional basis engineering enable the hole-driven levofloxacin oxidation at the interface of BTT fragments to occur, accompanying with electron-mediated oxygen reduction on terphenyl motif to active radicals, endowing it facilitate the balanced extraction of holes and electrons.

Cuprous-mediated peroxymonosulfate activation for Fenton-like removal of micropollutants: The function of co-catalyst and the accelerated degradation mechanism.

Introducing co-catalysts to enhance the activation of cuprous-mediated peroxymonosulfate (PMS) and induce the continuous generation of highly reactive oxygen species is promising. The function, effectiveness, and acceleration mechanism of co-catalysts in the cuprous-mediated PMS activation process were fully explored in this work, which focused on rhodamine B as the target contaminants. The results demonstrated that molybdenum (Mo) powder was a superb co-catalyst, and that the reaction of cuprous-mediated PMS system was carried out by surface Mo species as opposed to Mo ions in the solution. The Cu (II)/Cu(I) cycle was primarily encouraged by the Mo0, which also caused abundant ·HO and 1O2 and minimal SO4·- and ·O2- to be produced from PMS. The Mo/Cu2+/PMS system exhibited high removal efficiency towards typical pollutants, especially ciprofloxacin, methyl orange, malachite green, and crystal violet, with removal rates up to 93%, 99%, 97%, and 92%, respectively. Additionally, this system showed excellent adaptability to complex water environments. After four cycles, the Mo powder retained its properties and morphology, and the target pollutants could still maintain an 82% degradation efficiency. This study provides a basis for enhancing cuprous-mediated PMS activation for wastewater treatment.

Assisted wet deposition targeted synthesis of Co-N coordination single-atom catalysts for efficient Fenton-like catalytic degradation of micropollutants.

Assisted wet deposition methods to localize the active phase metal on the carrier surface and prevent atomic aggregation during conventional heat treatment are strongly preferred. Herein, single-atom cobalt catalysts (SA-Co-PCN) with different metal-central content were target-prepared using a combination of impregnation and secondary annealing on polymerized carbon nitride (PCN) through reticular confinement. Fitting the coordination configuration of the Co-N pathway within the first coordination shell according to quantitative EXAFS indicated that the ligancy of Co-N was 4. The removal efficiency of representative micropollutants in the SA-Co-PCN/PMS system achieved 100% within 15 min. The outstanding degradation properties of micropollutants were ascribed to the SA-Co-PCN boosts PMS to a 1O2-dominated system. Moreover, the effects of substituents on the degradation behavior and ecotoxicology of sulfonamides (SAs) in PMS-activated systems were investigated in depth. The combination of DFT theoretical calculations and LC-MS further confirmed that the similar electron-rich sites on the SAs molecules allowed for commonality in the degradation pathway. Both S-N bond and C-S bond fragments became the initial attack and cleavage sites in the series of SAs. Ecotoxicity predictions indicated that most intermediates of SAs exhibited lower acute and chronic toxicity, especially acute toxicity, than the parent compounds. ENVIRONMENTAL IMPLICATION: Assisted wet deposition to localize the active phase metal on the carrier surface allows easy target formation of single-atom cobalt catalysts (SA-Co-PCN), which could boost PMS to a 1O2-dominated system for efficient oxidation of typical micropollutants. The degradation behavior and ecotoxicology of sulfonamides in the SA-Co-PCN/PMS system were investigated in depth, revealing that most intermediates of sulfonamides exhibited lower acute and chronic toxicity, especially acute toxicity, than the parent compounds. This work provides a strategy for the development of facilely prepared single-atom catalysts and contributes to the development and application potential of PMS advanced oxidation technology for water pollution control.

Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis.

Constructing photocatalytically active and stable covalent organic frameworks containing both oxidative and reductive reaction centers remain a challenge. In this study, benzotrithiophene-based covalent organic frameworks with spatially separated redox centers are rationally designed for the photocatalytic production of hydrogen peroxide from water and oxygen without sacrificial agents. The triazine-containing framework demonstrates high selectivity for H2O2 photogeneration, with a yield rate of 2111 µM h-1 (21.11 µmol h-1 and 1407 µmol g-1 h-1) and a solar-to-chemical conversion efficiency of 0.296%. Codirectional charge transfer and large energetic differences between linkages and linkers are verified in the double donor-acceptor structures of periodic frameworks. The active sites are mainly concentrated on the electron-acceptor fragments near the imine bond, which regulate the electron distribution of adjacent carbon atoms to optimally reduce the Gibbs free energy of O2* and OOH* intermediates during the formation of H2O2.

Linkage Microenvironment of Azoles-Related Covalent Organic Frameworks Precisely Regulates Photocatalytic Generation of Hydrogen Peroxide.

Artificial H2 O2 photosynthesis by covalent organic frameworks (COFs) photocatalysts is promising for wastewater treatment. The effect of linkage chemistry of COFs as functional basis to photoelectrochemical properties and photocatalysis remains a significant challenge. In this study, three kinds of azoles-linked COFs including thiazole-linked TZ-COF, oxazole-linked OZ-COF and imidazole-linked IZ-COF were successfully synthesized. More accessible channels of charge transfer were constructed in TZ-COF via the donor-π-acceptor structure between thiazole linkage and pyrene linker, leading to efficient suppression of photoexcited charge recombination. Density functional theory calculations support the experimental studies, demonstrating that the thiazole linkage is more favorable for the formation of *O2 intermediate in H2 O2 production than that of the oxazole and imidazole linkages. The real active sites in COFs located at the benzene ring fragment between pyrene unit and azole linkage.

Physicochemical properties, metal availability and bacterial community structure in heavy metal-polluted soil remediated by montmorillonite-based amendments.

Clay materials are commonly used in remediation techniques for heavy metal contaminated soil. In this study, a magnesium (Mg(OH)2/MgO)-montmorillonite was proposed to be utilized for heavy metals immobilization in contaminated soil, with the remediation efficiency evaluated through the toxicity characteristic leaching procedure (TCLP) and the community bureau of reference sequential extraction procedure (BCR). The addition of magnesium-montmorillonite resulted in lower TCLP extractability for the heavy metals (Cu, Pb, Zn and Cd) in soil as it promoted their conversion from acid soluble fraction to residual fraction. Meanwhile, MM raised the soil pH and water-soluble organic carbon (WSOC). It was demonstrated that the immobilization of heavy metal in the presence of magnesium-montmorillonite was primarily induced by electrostatic attraction, precipitation and chelation with water-soluble organic carbon. Interestingly, a decreased bacterial community diversity was observed in soil treated by magnesium-montmorillonite (MM). The presence of pure magnesium-montmorillonite promoted the relative abundance of Proteobacteria, Actinobacteria and Firmicutes but reduced that of Bacteroides and Acidobacteria. Our results suggest that integrating the biochar into montmorillonite-based amendments can alleviate the damage to soil microorganisms by weakening the negative correlation between the two factors (content clay and WSOC in soil) and soil bacteria.