Unraveling charge transfer dynamics in AgBr/Bi4Ti3O12/Bi2Sn2O7 ternary S-scheme heterojunction photocatalyst.

In this study, AgBr/Bi4Ti3O12/Bi2Sn2O7 (ABr/BTO/BSO) composites were successfully synthesized to facilitate multi-channel fast charge transfer. This directs the charge carriers to travel along multichannel pathways and suppresses carrier recombination. The mechanisms underlying charge transfer in the dual S-scheme heterojunction composites were elucidated using density functional theory (DFT) and in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS). Furthermore, electron spin resonance (ESR) and burst experiments verified h+, ·O2 -, and ·OH as the primary active species in the catalytic process. The ABr/BTO/BSO composites demonstrated exceptional photocatalytic redox capabilities, completely degrading rhodamine B (RhB) and achieving degradation rates of 77.21% for tetracycline (TC) and 81.04% for Cr (VI). Both experimental and theoretical analyses confirmed the intrinsic efficacy of photo-induced electron movement within the composites. This research introduces innovative design concepts and strategies for the advanced exploration of electron channel transfer in ABr/BTO/BSO ternary composites and the development of novel composite photocatalytic systems.

Enhanced bioelectroremediation of heavy metal contaminated groundwater through advancing a self-standing cathode.

Hexavalent chromium (Cr(VI)) contamination in groundwater poses a substantial global challenge due to its high toxicity and extensive industrial applications. While the bioelectroremediation of Cr(VI) has attracted huge attention for its eco-friendly attributes, its practical application remains constrained by the hydrogeochemical conditions of groundwater (mainly pH), low electron transfer efficiency, limitations in electrocatalyst synthesis and electrode fabrication. In this study, we developed and investigated the use of N, S co-doped carbon nanofibers (CNFs) integrated on a graphite felt (GF) as a self-standing cathode (NS/CNF-GF) for the comprehensive reduction of Cr(VI) from real contaminated groundwater. The binder free cathode, prepared through electro-polymerization, was employed in a dual-chamber microbial fuel cell (MFC) for the treatment of Cr (VI)-laden real groundwater (40 mg/L) with a pH of 7.4. The electrochemical characterization of the prepared cathode revealed a distinct electroactive surface area, more wettability, facilitating enhanced adsorption and rapid electron transfer, resulting in a commendable Cr(VI) reduction rate of 0.83 mg/L/h. The MFC equipped with NS/CNF-GF demonstrated the lowest charge transfer resistance (Rct) and generated the highest power density (155 ± 0.3 mW/m2) compared to control systems. The favorable electrokinetics for modified cathode led to swift substrate consumption in the anode, releasing more electrons and protons, thereby accelerating Cr(VI) reduction to achieve the highest cathodic coulombic efficiency (C.Eca)of80 ± 1.3 %. A similar temporal trend observed between Cr(VI) removal efficiency, COD removal efficiency, and C.Eca, underscores the effective performance of the modified electrode. The reusability of the binder free cathode, exemption from catholyte preparation and the absence of pH regulation requirements highlighted the potential scalability and applicability of our findings on a larger scale.

Processes and mechanisms in remediation of aqueous chromium contamination by sulfidated nano-scale zerovalent iron (S-nZVI): Experimental and computational investigations.

Sulfidated nano-scale zerovalent iron (S-nZVI) has emerged as an advanced functional nanomaterial for efficiently remediating Cr(VI) contamination in aqueous environments. However, there is an insufficient understanding of its coherent process, removal pathway, and hydrochemical reactive mechanisms, presenting potential challenges for its future environmental applications. To address this gap, this study successfully synthesized S-nZVI through a chemical precipitation method and effectively applied it for the removal of Cr(VI). Additional characterization revealed that the removal of Cr(VI) followed a sequence of rapid chemisorption and intraparticle diffusion processes, concomitant with an increase in pH and a decrease in oxidation-reduction potential. The remediation mechanism encompassed a synergistic reduction of Cr(VI) to Cr(III) and simultaneous immobilization via Cr2FeO4 coprecipitation. The highest Cr(VI) removal capacity of 75 mg/g was attained during dynamic removal experiments in the sand column packed with S-nZVI. Further computational analysis, employing density functional theory calculations based on the experimental data, revealed the involvement of multiple molecular orbitals of Cr(VI) in the removal process. It also elucidated a step-by-step reduction pathway for Cr(VI) characterized by decreasing free energy. These findings provide evidence-based insights into Cr(VI) remediation using S-nZVI and can serve as valuable technical support for future environmental management of heavy metals.

An integrated approach using ozone nanobubble and cyclodextrin inclusion complexation to enhance the removal of micropollutants.

Ozone (O3) has been widely used for the elimination of recalcitrant micropollutants in aqueous environments, due to its strong oxidation ability. However, the utilization efficiency of O3 is constrained by its low solubility and short half-life during the treatment process. Herein, an integrated approach, using nanobubble technology and micro-environmental chemistry within cyclodextrin inclusion cavities, was studied in order to enhance the reactivity of ozonisation. Compared with traditional macrobubble aeration with O3 in water, nanobubble aeration achieved 1.7 times higher solubility of O3, and increased the mass transfer coefficient 4.7 times. Moreover, the addition of hydroxypropyl-ß-cyclodextrin (HPßCD) further increased the stability of O3 through formation of an inclusion complex in its molecule-specific cavity. At a HPßCD:O3 molar ratio of 10:1, the lifespan of O3 reached 18 times longer than in a HPßCD-free O3 solution. Such approach accelerated the removal efficiency of the model micropollutant, 4-chlorophenol by 6.9 times, compared with conventional macrobubble ozonation. Examination of the HPßCD inclusion complex by UV-visible spectroscopy and Nuclear Magnetic Resonance analyses revealed that both O3 and 4-chlorophenol entered the HPßCD cavity, and Benesi-Hildebrand plots indicated a 1:1 stoichiometry of the host and guest compounds. Additionally, molecular docking simulations were conducted in order to confirm the formation of a ternary complex of HPßCD:4-chlorophenol:O3 and to determine the optimal inclusion mode. With these results, our study highlights the viability of the proposed integrated approach to enhance the ozonation of organic micropollutants.

Intensifying ozonation treatment of municipal secondary effluent using a combination of microbubbles and ultraviolet irradiation.

Ozonation treatment of municipal secondary effluent is complicated by the low solubility of ozone and inefficient production of hydroxyl free radicals from ozone decomposition. To resolve these problems, this study investigated methods for intensifying ozonation treatment, using a combination of microbubbles and ultraviolet (UV) irradiation (UV/MBO). The high efficiency of the method was illustrated by treating river water containing refractory components derived from secondary effluent in a wastewater treatment plant. The results showed that the ozone mass transfer coefficient in a microbubble system was an order of magnitude compared with a conventional macrobubble system at the initial stage. The amount of ·OH generated during the treatment was quantified using a fluorescent probe analysis. The amount of ·OH in the UV/MBO system was almost 2-6 times more than the amount found with conventional ozonation using macrobubbles (CO), CO with UV irradiation (UV/CO), and microbubble ozonation (MBO) units. The UV/MBO system achieved chemical oxygen demand (COD), UV254, and UV400 removal performance rates of up to 37.50%, 81.15%, and 94.74% respectively. These levels were 2-36% higher than those in other systems. The coupling UV/MBO treatment significantly reduced all five categories of substances according to EEM spectra and fluorescence regional integration. The distribution of fractions with different molecular weights (MW) was altered and the UV254 of MW (< 500 Da) increased by 15.8%. The biodegradability of the water was significantly improved, as indicated by the TOC/UV254. This is ascribed to the enhanced degradation of refractory organics in the water. The combination of the UV/microbubble technique with ozonation could provide an efficient approach for advanced wastewater treatment. Graphical abstract.