DFT Predirected Molecular Engineering Design of Donor-Acceptor Structured g-C3N4 for Efficient Photocatalytic Tetracycline Abatement.

The photocatalytic environmental decontamination ability of carbon nitride (g-C3N4, CN) typically suffers from their inherent structural defects, causing rapid recombination of photogenerated carriers. Conjugating CN with tailored donor-acceptor (D-A) units to counteract this problem through electronic restructuring becomes a feasible strategy, where confirmation by density functional theory (DFT) calculations becomes indispensable. Herein, DFT is employed to predirect the copolymerization modification of CN by benzene derivatives, screening benzaldehyde as the optimal electron-donating candidate for the construction of reoriented intramolecular charge transfer path. Experimental characterization and testing corroborate the formation of a narrowed bandgap as well as high photoinduced carrier separation. Consequently, the optimal BzCN-2 exhibited superior photocatalytic capacity in application for tetracycline hydrochloride degradation, with 3.73 times higher than that of CN. Besides, the BzCN-2-based photocatalytic system is determined to have a toxicity-mitigating effect on TC removal via T.E.S.T and prefers the removal of dissociable TC2- species under partial alkalinity. This work provides insight into DFT guidance for the design of D-A conjugated polymer and its application scenarios in photocatalytic decontamination.

Periodate activated by manganese oxide/biochar composites for antibiotic degradation in aqueous system: Combined effects of active manganese species and biochar.

Developing efficient catalysts for oxytetracycline (OTC) degradation is an ideal strategy to tackle environmental pollution, and advanced oxidation processes (AOPs) have been widely used for its degradation. However, the studies on the activation of periodate (PI) by biochar and its composites in recent years have been scarcely reported. In this study, we focused on the degradation of OTC by PI activation with manganese oxide/biochar composites (MnxOy@BC). Experimental results showed that the OTC degradation rate of MnxOy@BC/PI system reached almost 98%, and the TOC removal efficiency reached 75%. Various characteristic analysis proved that PI could be activated efficiently by surface functional groups and manganese-active species (Mn(II), Mn(III), and Mn(IV)) on biochar, and various reactive species such as singlet oxygen (1O2), hydroxyl radical (∙OH), and superoxide radical (O2∙-) can be observed via radical quenching experiments. Based on this, three degradation pathways were proposed. Furthermore, MnxOy@BC and PI were combined to degrade environmental pollutants, which achieved excellent practical benefits and had great practical application potential. We hope that it can provide new ideas for advanced oxidation processes (AOPs) applying for wastewater treatment in the future.