Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

Simultaneous removal of NOx and chlorobenzene on V2O5/TiO2 granular catalyst: Kinetic study and performance prediction

• A V₂O₅/TiO₂ granular catalyst for simultaneous removal of NO and chlorobenzene. • Catalyst synthesized by vanadyl acetylacetonate showed good activity and stability. • The kinetic model was established and the synergetic activity was predicted. • Both chlorobenzene oxidation and SCR of NO follow pseudo-first-order kinetics. • The work is of much value to design of multi-pollutants emission control system. The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology, which is still in the initial stage and facing many challenges. We developed a V₂O₅/TiO₂ granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene (i.e., an important precursor of dioxins). The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability. Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited, the reaction order of each reaction was not considerably affected, and the pseudo-first-order reaction kinetics was still followed. The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants (i.e., NO and dioxins) emission control.     

Electro-catalytic activity of CeOx modified graphite felt for carbamazepine degradation via E-peroxone process

•CeO_x/GF-EP process had the better degradation efficiency than GF-EP process. •CeO_x/GF-EP process had the flexible application in the pH range from 5.0 to 9.0. •CeO_x could enhance surface hydrophilicity and reduce the charge-transfer resistance. •The interfacial electron transfer process was revealed. E-peroxone (EP) was one of the most attractive AOPs for removing refractory organic compounds from water, but the high energy consumption for in situ generating H₂O₂ and its low reaction efficiency for activating O₃ under acidic conditions made the obstacles for its practical application. In this study, cerium oxide was loaded on the surface of graphite felt (GF) by the hydrothermal method to construct the efficient electrode (CeO_x/GF) for mineralizing carbamazepine (CBZ) via EP process. CeO_x/GF was an efficient cathode, which led to 69.4% TOC removal in CeO_x/GF-EP process with current intensity of 10 mA in 60 min. Moreover, CeO_x/GF had the flexible application in the pH range from 5.0 to 9.0, TOC removal had no obvious decline with decrease of pH. Comparative characterizations showed that CeO_x could enhance surface hydrophilicity and reduce the charge-transfer resistance of GF. About 5.4 mg/L H₂O₂ generated in CeO_x/GF-EP process, which was 2.1 times as that in GF-EP process. The greater ozone utility was also found in CeO_x/GF-EP process. More O₃ was activated into hydroxyl radicals, which accounted for the mineralization of CBZ. An interfacial electron transfer process was revealed, which involved the function of oxygen vacancies and Ce³⁺/Ce⁴⁺ redox cycle. CeO_x/GF had the good recycling property in fifth times’ use.     

Hydroxyl radical intensified Cu2O NPs/H2O2 process in ceramic membrane reactor for degradation on DMAc wastewater from polymeric membrane manufacturer

• Cu₂O NPs/H₂O₂ Fenton process was intensified by membrane dispersion. • DMAc removal was enhanced to 98% for initial DMAc of 14000 mg/L. • Analyzed time-resolved degradation pathway of DMAc under ·OH attack. High-concentration industrial wastewater containing N,N-dimethylacetamide (DMAc) from polymeric membrane manufacturer was degraded in Cu₂O NPs/H₂O₂ Fenton process. In the membrane-assisted Fenton process DMAc removal rate was up to 98% with 120 min which was increased by 23% over the batch reactor. It was found that ·OH quench time was extended by 20 min and the maximum ·OH productivity was notably 88.7% higher at 40 min. The degradation reaction rate constant was enhanced by 2.2 times with membrane dispersion (k = 0.0349 min⁻¹). DMAc initial concentration (C₀) and H₂O₂ flux (J_p) had major influence on mass transfer and kinetics, meanwhile, membrane pore size (r_p) and length (L_m) also affected the reaction rate. The intensified radical yield, fast mass transfer and nanoparticles high activity all contributed to improve pollutant degradation efficiency. Time-resolved DMAc degradation pathway was analyzed as hydroxylation, demethylation and oxidation leading to the final products of CO₂, H₂O and NO₃⁻ (rather than NH₃ from biodegradation). Continuous process was operated in the dual-membrane configuration with in situ reaction and separation. After five cycling tests, DMAc removal was all above 95% for the initial [DMAc]₀ = 14,000 mg/L in wastewater and stability of the catalyst and the membrane maintained well.     

Enhanced 4-chlorophenol biodegradation by integrating Fe2O3 nanoparticles into an anaerobic reactor: Long-term performance and underlying mechanism

• 4-chlorophenol biodegradation could be enhanced in Fe₂O₃ coupled anaerobic system. • Metabolic activity and electron transport could be improved by Fe₂O₃ nanoparticles. • Functional microbial communities could be enriched in coupled anaerobic system. • Possible synergistic mechanism involved in enhanced dechlorination was proposed. Fe₂O₃ nanoparticles have been reported to enhance the dechlorination performance of anaerobic systems, but the underlying mechanism has not been clarified. This study evaluated the technical feasibility, system stability, microbial biodiversity and the underlying mechanism involved in a Fe₂O₃ nanoparticle-coupled anaerobic system treating 4-chlorophenol (4-CP) wastewater. The results demonstrated that the 4-CP and total organic carbon (TOC) removal efficiencies in the Fe₂O₃-coupled up-flow anaerobic sludge blanket (UASB) were always higher than 97% and 90% during long-term operation, verifying the long-term stability of the Fe₂O₃-coupled UASB. The 4-CP and TOC removal efficiencies in the coupled UASB increased by 42.9±0.4% and 27.5±0.7% compared to the control UASB system. Adding Fe₂O₃ nanoparticles promoted the enrichment of species involved in dechlorination, fermentation, electron transfer and acetoclastic methanogenesis, and significantly enhanced the extracellular electron transfer ability, electron transport activity and conductivity of anaerobic sludge, leading to enhanced 4-CP biodegradation performance. A possible synergistic mechanism involved in enhanced anaerobic 4-CP biodegradation by Fe₂O₃ nanoparticles was proposed.     

Enhanced catalytic oxidation of 2,4-dichlorophenol via singlet oxygen dominated peroxymonosulfate activation on CoOOH@Bi2O3 composite

• Bi₂O₃ cannot directly activate PMS. • Bi₂O₃ loading increased the specific surface area and conductivity of CoOOH. • Larger specific surface area provided more active sites for PMS activation. • Faster electron transfer rate promoted the generation of reactive oxygen species. • ¹O₂ was identified as dominant ROS in the CoOOH@Bi₂O₃/PMS system. Cobalt oxyhydroxide (CoOOH) has been turned out to be a high-efficiency catalyst for peroxymonosulfate (PMS) activation. In this study, CoOOH was loaded on bismuth oxide (Bi₂O₃) using a facile chemical precipitation process to improve its catalytic activity and stability. The result showed that the catalytic performance on the 2,4-dichlorophenol (2,4-DCP) degradation was significantly enhanced with only 11 wt% Bi₂O₃ loading. The degradation rate in the CoOOH@Bi₂O₃/PMS system (0.2011 min⁻¹) was nearly 6.0 times higher than that in the CoOOH/PMS system (0.0337 min⁻¹). Furthermore, CoOOH@Bi₂O₃ displayed better stability with less Co ions leaching (16.4% lower than CoOOH) in the PMS system. These phenomena were attributed to the Bi₂O₃ loading which significantly increased the conductivity and specific surface area of the CoOOH@Bi₂O₃ composite. Faster electron transfer facilitated the redox reaction of Co (III) / Co (II) and thus was more favorable for reactive oxygen species (ROS) generation. Meanwhile, larger specific surface area furnished more active sites for PMS activation. More importantly, there were both non-radical (¹O₂) and radicals (SO₄⁻•, O₂⁻•, and OH•) in the CoOOH@Bi₂O₃/PMS system and ¹O₂ was the dominant one. In general, this study provided a simple and practical strategy to enhance the catalytic activity and stability of cobalt oxyhydroxide in the PMS system.     

One-pot hydrothermal fabrication of BiVO4/Fe3O4/rGO composite photocatalyst for the simulated solar light-driven degradation of Rhodamine B

• BiVO₄/Fe₃O₄/rGO has excellent photocatalytic activity under solar light radiation. • It can be easily separated and collected from water in an external magnetic field. • BiVO₄/Fe₃O₄/0.5% rGO exhibited the highest RhB removal efficiency of over 99%. • Hole (h⁺) and superoxide radical (O₂^•−) dominate RhB photo-decomposition process. • The reusability of this composite was confirmed by five successive recycling runs. Fabrication of easily recyclable photocatalyst with excellent photocatalytic activity for degradation of organic pollutants in wastewater is highly desirable for practical application. In this study, a novel ternary magnetic photocatalyst BiVO₄/Fe₃O₄/reduced graphene oxide (BiVO₄/Fe₃O₄/rGO) was synthesized via a facile hydrothermal strategy. The BiVO₄/Fe₃O₄ with 0.5 wt% of rGO (BiVO₄/Fe₃O₄/0.5% rGO) exhibited superior activity, degrading greater than 99% Rhodamine B (RhB) after 120 min solar light radiation. The surface morphology and chemical composition of BiVO₄/Fe₃O₄/rGO were studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–visible diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The free radicals scavenging experiments demonstrated that hole (h⁺) and superoxide radical (O₂^•−) were the dominant species for RhB degradation over BiVO₄/Fe₃O₄/rGO under solar light. The reusability of this composite catalyst was also investigated after five successive runs under an external magnetic field. The BiVO₄/Fe₃O₄/rGO composite was easily separated, and the recycled catalyst retained high photocatalytic activity. This study demonstrates that catalyst BiVO₄/Fe₃O₄/rGO possessed high dye removal efficiency in water treatment with excellent recyclability from water after use. The current study provides a possibility for more practical and sustainable photocatalytic process.     

Size and shape effects of MnFe2O4 nanoparticles as catalysts for reductive degradation of dye pollutants

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method. • Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs. • The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied. • The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior. • All the MnFe₂O₄ NPs exhibit selective degradation to different dyes. The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.     

Oxidation and biotoxicity assessment of microcystin-LR using different AOPs based on UV,O3 and H2O2

MC-LR removal performances under different AOPs were compared systematically. Higher removal efficiency and synergistic effects were obtained by combined process. The acute biotoxicity raised in different degrees after oxidation. Microcystin-LR attracts attention due to its high toxicity, high concentration and high frequency. The removal characteristics of UV/H₂O₂ and O₃/H₂O₂ advanced oxidation processes and their individual process for MC-LR were investigated and compared in this study. Both the removal efficiencies and rates of MC-LR as well as the biotoxicity of degradation products was analyzed. Results showed that the UV/H₂O₂ process and O₃/H₂O₂ were effective methods to remove MC-LR from water, and they two performed better than UV-, O₃-, H₂O₂-alone processes under the same conditions. The effects of UV intensity, H₂O₂ concentration and O₃ concentration on the removal performance were explored. The synergistic effects between UV and H₂O₂, O₃ and H₂O₂ were observed. UV dosage of 1800 mJ·cm⁻² was required to remove 90% of 100 mg·L⁻¹ MC-LR, which amount significantly decreased to 500 mJ·cm⁻² when 1.7 mg·L⁻¹ H₂O₂ was added. 0.25 mg·L⁻¹ O₃, or 0.125 mg·L⁻¹ O₃ with 1.7 mg·L⁻¹ H₂O₂ was needed to reach 90% removal efficiency. Furthermore, the biotoxicity results about these UV/H₂O₂, O₃/H₂O₂ and O₃-alone processes all present rising trends with oxidation degree of MC-LR. Biotoxicity of solution, equivalent to 0.01 mg·L⁻¹ Zn²⁺, raised to 0.05 mg·L⁻¹ Zn²⁺ after UV/H₂O₂ or O₃/H₂O₂ reaction. This phenomenon may be attributed to the aldehydes and ketones with small molecular weight generated during reaction. Advice about the selection of MC-LR removal methods in real cases was provided.     

Mercury removal from aqueous solution using petal-like MoS2 nanosheets

• Synthesized few-layered MoS₂ nanosheets via surfactant-assisted hydrothermal method. • Synthesized MoS₂ nanosheets show petal-like morphology. • Adsorbent showed 93% of mercury removal efficiency. • The adsorption of mercury is attributed to negative zeta potential (-21.8 mV). Recently, different nanomaterial-based adsorbents have received greater attention for the removal of environmental pollutants, specifically heavy metals from aqueous media. In this work, we synthesized few-layered MoS₂ nanosheets via a surfactant-assisted hydrothermal method and utilized them as an efficient adsorbent for the removal of mercury from aqueous media. The synthesized MoS₂ nanosheets showed petal-like morphology as confirmed by scanning electron microscope and high-resolution transmission electron microscopic analysis. The average thickness of the nanosheets is found to be about 57 nm. Possessing high stability and negative zeta potential makes this material suitable for efficient adsorption of mercury from aqueous media. The adsorption efficiency of the adsorbent was investigated as a function of pH, contact time and adsorbent dose. The kinetics of adsorption and reusability potential of the adsorbent were also performed. A pseudo-second-order kinetics for mercury adsorption was observed. As prepared MoS₂ nanosheets showed 93% mercury removal efficiency, whereas regenerated adsorbent showed 91% and 79% removal efficiency in the respective 2^nd and 3^rd cycles. The adsorption capacity of the adsorbent was found to be 289 mg/g at room temperature.     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

Degradation of refractory organics in concentrated leachate by the Fenton process: Central composite design for process optimization

• 90% total COD, 95.3% inert COD and 97.2% UV₂₅₄ were removed. • High R² values (over 95%) for all responses were obtained with CCD. • Operational cost was calculated to be 0.238 €/g COD_removed for total COD removal. • Fenton oxidation was highly-efficient method for inert COD removal. • BOD₅/COD ratio of leachate concentrate raised from 0.04 to 0.4. The primary aim of this study is inert COD removal from leachate nanofiltration concentrate because of its high concentration of resistant organic pollutants. Within this framework, this study focuses on the treatability of leachate nanofiltration concentrate through Fenton oxidation and optimization of process parameters to reach the maximum pollutant removal by using response surface methodology (RSM). Initial pH, Fe²⁺ concentration, H₂O₂/Fe²⁺ molar ratio and oxidation time are selected as the independent variables, whereas total COD, color, inert COD and UV₂₅₄ removal are selected as the responses. According to the ANOVA results, the R² values of all responses are found to be over 95%. Under the optimum conditions determined by the model (pH: 3.99, Fe²⁺: 150 mmol/L, H₂O₂/Fe²⁺: 3.27 and oxidation time: 84.8 min), the maximum COD removal efficiency is determined as 91.4% by the model. The color, inert COD and UV₂₅₄ removal efficiencies are determined to be 99.9%, 97.2% and 99.5%, respectively, by the model, whereas the total COD, color, inert COD and UV₂₅₄ removal efficiencies are found respectively to be 90%, 96.5%, 95.3% and 97.2%, experimentally under the optimum operating conditions. The Fenton process improves the biodegradability of the leachate NF concentrate, increasing the BOD₅/COD ratio from the value of 0.04 to the value of 0.4. The operational cost of the process is calculated to be 0.238 €/g COD_removed. The results indicate that the Fenton oxidation process is an efficient and economical technology in improvement of the biological degradability of leachate nanofiltration concentrate and in removal of resistant organic pollutants.     

One-step ball milling-prepared nano Fe2O3 and nitrogen-doped graphene with high oxygen reduction activity and its application in microbial fuel cells

• Nano Fe₂O₃ and N-doped graphene was prepared via a one-step ball milling method. • The maximum power density of Fe-N-G in MFC was 390% of that of pristine graphite. • Active sites like nano Fe₂O₃, pyridinic N and Fe-N groups were formed in Fe-N-G. • The improvement of Fe-N-G was due to full exposure of active sites on graphene. Developing high activity, low-cost and long durability catalysts for oxygen reduction reaction is of great significance for the practical application of microbial fuel cells. The full exposure of active sites in catalysts can enhance catalytic activity dramatically. Here, novel Fe-N-doped graphene is successfully synthesized via a one-step in situ ball milling method. Pristine graphite, ball milling graphene, N-doped graphene and Fe-N-doped graphene are applied in air cathodes, and enhanced performance is observed in microbial fuel cells with graphene-based catalysts. Particularly, Fe-N-doped graphene achieves the highest oxygen reduction reaction activity, with a maximum power density of 1380±20 mW/m² in microbial fuel cells and a current density of 23.8 A/m² at –0.16 V in electrochemical tests, which are comparable to commercial Pt and 390% and 640% of those of pristine graphite. An investigation of the material characteristics reveals that the superior performance of Fe-N-doped graphene results from the full exposure of Fe₂O₃ nanoparticles, pyrrolic N, pyridinic N and excellent Fe-N-G active sites on the graphene matrix. This work not only suggests the strategy of maximally exposing active sites to optimize the potential of catalysts but also provides promising catalysts for the use of microbial fuel cells in sustainable energy generation.     

Remediation of 2,4-dichlorophenol-contaminated groundwater using nano-sized CaO2 in a two-dimensional scale tank

• Nano CaO₂ is evaluated as a remediation agent for 2,4-DCP contaminated groundwater. • 2,4-DCP degradation mechanism by different Fe²⁺ concentration was proposed. • 2,4-DCP was not degraded in the system for solution pH>10. • The 2,4-DCP degradation area is inconsistent with the nano CaO₂ distribution area. This study evaluates the applicability of nano-sized calcium peroxide (CaO₂) as a source of H₂O₂ to remediate 2,4-dichlorophenol (2,4-DCP) contaminated groundwater via the advanced oxidation process (AOP). First, the effect and mechanism of 2,4-DCP degradation by CaO₂ at different Fe concentrations were studied (Fenton reaction). We found that at high Fe concentrations, 2,4-DCP almost completely degrades via primarily the oxidation of •OH within 5 h. At low Fe concentrations, the degradation rate of 2,4-DCP decreased rapidly. The main mechanism was the combined action of •OH and O₂^•−. Without Fe, the 2,4-DCP degradation reached 13.6% in 213 h, primarily via the heterogeneous reaction on the surface of CaO₂. Besides, 2,4-DCP degradation was significantly affected by solution pH. When the solution pH was>10, the degradation was almost completely inhibited. Thus, we adopted a two-dimensional water tank experiment to study the remediation efficiency CaO₂ on the water sample. We noticed that the degradation took place mainly in regions of pH<10 (i.e., CaO₂ distribution area), both upstream and downstream of the tank. After 28 days of treatment, the average 2,4-DCP degradation level was ≈36.5%. Given the inadequacy of the results, we recommend that groundwater remediation using nano CaO₂: (1) a buffer solution should be added to retard the rapid increase in pH, and (2) the nano CaO₂ should be injected copiously in batches to reduce CaO₂ deposition.     

Utilizing transparent and conductive SnO2 as electron mediator to enhance the photocatalytic performance of Z-scheme Si-SnO2-TiOx

• A novel Z-scheme Si-SnO₂-TiO_x with SnO₂ as electron mediator is first constructed. • Transparent and conductive SnO₂ can pass light through and promote charge transport. • V_O from SnO₂ and TiO_x improve photoelectrochemical performances. • Efficient photocatalytic degradations originate from the Z scheme construction. Z-scheme photocatalysts, with strong redox ability, have a great potential for pollutants degradation. However, it is challenging to construct efficient Z-scheme photocatalysts because of their poor interfacial charge separation. Herein, by employing transparent and conductive SnO₂ as electron mediator to pass light through and promote interfacial charge transportation, a novel Z-scheme photocatalyst Si-SnO₂-TiO_{x (1<x<2)} was constructed. The Z-scheme photocatalyst displayed an order of magnitude higher photocurrent density and a 4-fold increase in open-circuit potential compared to those of Si. Moreover, the onset potential shifted negatively for approximately 2.2 V. Benefiting from these advantages, this Z-scheme Si-SnO₂-TiO_x exhibited efficient photocatalytic performance toward phenol degradation and mineralization. 75% of the phenol was degraded without bias potential and 70% of the TOC was removed during phenol degradation. Other typical pollutants such as bisphenol A and atrazine could also be degraded without bias potential. Introducing a transparent and conductive electron mediator to construct Z-scheme photocatalyst gives a new sight to the improvement of photocatalytic performance in Z scheme.     

A pulsed switching peroxi-coagulation process to control hydroxyl radical production and to enhance 2,4-Dichlorophenoxyacetic acid degradation

• A new pulsed switching peroxi-coagulation (PSPC) system was developed. • The EC_T for 2,4-D removal in the PSPC was lower than that in the EF. • The iron consumption for 2,4-D removal in the PSPC was lower than that in the PC. The aim of this study was to develop a new pulsed switching peroxi-coagulation system to control hydroxyl radical (?OH) production and to enhance 2,4-Dichlorophenoxyacetic acid (2,4-D) degradation. The system was constructed with a sacrifice iron anode, a Pt anode, and a gas diffusion cathode. Production of H₂O₂ and Fe²⁺ was controlled separately by time delayers with different pulsed switching frequencies. Under current densities of 5.0 mA/cm² (H₂O₂) and 0.5 mA/cm² (Fe²⁺), the ?OH production was optimized with the pulsed switching frequency of 1.0 s (H₂O₂):0.3 s (Fe²⁺) and the ratio of H₂O₂ to Fe²⁺ molar concentrations of 6.6. Under the optimal condition, 2,4-D with an initial concentration of 500 mg/L was completely removed in the system within 240 min. The energy consumption for the 2,4-D removal in the system was much lower than that in the electro-Fenton process (68±6 vs. 136±10 kWh/kg TOC). The iron consumption in the system was ~20 times as low as that in the peroxi-coagulation process (196±20 vs. 3940±400 mg/L) within 240 min. The system should be a promising peroxi-coagulation method for organic pollutants removal in wastewater.     

Enhancement of the polynomial functions response surface model for real-time analyzing ozone sensitivity

• The calculation process and algorithm of response surface model (RSM) were enhanced. • The prediction errors of RSM in the margin and transition areas were greatly reduced. • The enhanced RSM was able to analyze O₃-NO_x-VOC sensitivity in real-time. • The O₃ formations were mainly sensitive to VOC, for the two case study regions. Quantification of the nonlinearities between ambient ozone (O₃) and the emissions of nitrogen oxides (NO_x) and volatile organic compound (VOC) is a prerequisite for an effective O₃ control strategy. An Enhanced polynomial functions Response Surface Model (Epf-RSM) with the capability to analyze O₃-NO_x-VOC sensitivities in real time was developed by integrating the hill-climbing adaptive method into the optimized Extended Response Surface Model (ERSM) system. The Epf-RSM could single out the best suited polynomial function for each grid cell to quantify the responses of O₃ concentrations to precursor emission changes. Several comparisons between Epf-RSM and pf-ERSM (polynomial functions based ERSM) were performed using out-of-sample validation, together with comparisons of the spatial distribution and the Empirical Kinetic Modeling Approach diagrams. The comparison results showed that Epf-RSM effectively addressed the drawbacks of pf-ERSM with respect to over-fitting in the margin areas and high biases in the transition areas. The O₃ concentrations predicted by Epf-RSM agreed well with Community Multi-scale Air Quality simulation results. The case study results in the Pearl River Delta and the north-western area of the Shandong province indicated that the O₃ formations in the central areas of both the regions were more sensitive to anthropogenic VOC in January, April, and October, while more NO_x-sensitive in July.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Enhancement of the electrocatalytic oxidation of antibiotic wastewater over the conductive black carbon-PbO2 electrode prepared using novel green approach

• A novel conductive carbon black modified lead dioxide electrode is synthesized. • The modified PbO₂ electrode exhibits enhanced electrochemical performances. • BBD method could predict optimal experiment conditions accurately and reliably. • The modified electrode possesses outstanding reusability and safety. The secondary pollution caused by modification of an electrode due to doping of harmful materials has long been a big concern. In this study, an environmentally friendly material, conductive carbon black, was adopted for modification of lead dioxide electrode (PbO₂). It was observed that the as-prepared conductive carbon black modified electrode (C-PbO₂) exhibited an enhanced electrocatalytical performance and more stable structure than a pristine PbO₂ electrode, and the removal efficiency of metronidazole (MNZ) and COD by a 1.0% C-PbO₂ electrode at optimal conditions was increased by 24.66% and 7.01%, respectively. Results revealed that the electrochemical degradation of MNZ wastewater followed pseudo-first-order kinetics. This intimates that the presence of conductive carbon black could improve the current efficiency, promote the generation of hydroxyl radicals, and accelerate the removal of MNZ through oxidation. In addition, MNZ degradation pathways through a C-PbO₂ electrode were proposed based on the identified intermediates. To promote the electrode to treat antibiotic wastewater, optimal experimental conditions were predicted through the Box-Behnken design (BBD) method. The results of this study suggest that a C-PbO₂ electrode may represent a promising functional material to pretreat antibiotic wastewaters.