Visible-light-driven heterostructured g-C3N4/Bi-TiO2 floating photocatalyst with enhanced charge carrier separation for photocatalytic inactivation of Microcystis aeruginosa

• Bi doping in TiO₂ enhanced the separation of photo-generated electron-hole. • The performance of photocatalytic degradation of MC-LR was improved. • Coexisting substances have no influence on algal removal performance. • The key reactive oxygen species were h⁺ and ^•OH in the photocatalytic process. The increase in occurrence and severity of cyanobacteria blooms is causing increasing concern; moreover, human and animal health is affected by the toxic effects of Microcystin-LR released into the water. In this paper, a floating photocatalyst for the photocatalytic inactivation of the harmful algae Microcystis aeruginosa (M. aeruginosa) was prepared using a simple sol-gel method, i.e., coating g-C₃N₄ coupled with Bi-doped TiO₂ on Al₂O₃-modified expanded perlite (CBTA for short). The impact of different molar ratios of Bi/Ti on CBTA was considered. The results indicated that Bi doping in TiO₂ inhibited photogenerated electron-hole pair recombination. With 6 h of visible light illumination, 75.9% of M. aeruginosa (initial concentration= 2.7 × 10⁶ cells/L) and 83.7% of Microcystin-LR (initial concentration= 100 μg/L) could be removed with the addition of 2 g/L CBTA-1% (i.e., Bi/Ti molar ratio= 1%). The key reactive oxygen species (ROSs) in the photocatalytic inactivation process are h⁺ and ^•OH. The induction of the Bi⁴⁺/Bi³⁺ species by the incorporation of Bi could narrow the bandgap of TiO₂, trap electrons, and enhance the stability of CBTA-1% in the solutions with coexisting environmental substances.     

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

• The optimum SCR activity was realized by tuning the acid pretreatment. • Optimized catalysts showed NO_x conversion above 90%. • The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe. • The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction. Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.     

Catalytic urea hydrolysis by composite metal oxide catalyst towards efficient urea-based SCR process: performance evaluation and mechanism investigation

● Bimetallic oxide composite catalyst was designed for the urea-based SCR process. ● Surface chemical state and typical microstructure of catalyst was determined. ● Reaction route was improved based on intermediates and active site identification. ● TiO₂@Al₂O₃ presents an obvious promotion for urea hydrolysis. As a promising option to provide gaseous NH₃ for SCR system, catalytic urea hydrolysis has aroused great attention, and improving surface area and activity of catalysis are the crucial issues to be solved for efficient urea hydrolysis. Therefore, a composite metal oxide (TiO₂@Al₂O₃) catalyst was prepared by a simple hydrothermal method, with mesoporous alumina (γ-Al₂O₃) as substrate. The results verify the mesoporous structure and submicron cluster of TiO₂@Al₂O₃, with exposed crystal faces of (101) and (400) for TiO₂ and γ-Al₂O₃, respectively. The electronegativity difference of Ti⁴⁺ and Al³⁺ changes the charge distribution scheme around the interface, which provides abundant acid/base sites to boost the urea hydrolysis. Consequently, for an optimal proportioning with nano TiO₂ content at 10 wt.%, the hydrolysis efficiency can reach up to 35.2 % at 100 °C in 2 h, increasing by ~7.1 % than that of the blank experiment. ¹³C NMR spectrum measurements provide the impossible intermediate species during urea hydrolysis. Theoretical calculations are performed to clarify the efficient H₂O decomposition at the interface of TiO₂@Al₂O₃. The result offers a favorable technology for energy-efficiency urea hydrolysis.     

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.     

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.     

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.     

Development of highly active coated monolith SCR catalyst with strong abrasion resistance for low-temperature application

Monolith SCR catalysts coated with V₂O₅-WO₃/TiO₂ were prepared by varying binder and coating thickness. Comparing with a monolith extruded with 100% V₂O₅-WO₃/TiO₂ powder, a coated monolith with a catalyst-coating layer of 260 μm in thickness exhibited the similar initial NO_x reduction activity at 250°C. After 4 h abrasion (attrition) in an air stream containing 300 g·m⁻³ fine sands (50–100 μm) at a superficial gas velocity of 10 m·s⁻¹, the catalyst still has the activity as a 100% molded monolith does in a 24-h activity test and it retains about 92% of its initial activity at 250°C. Estimation of the equivalent durable hours at a fly ash concentration of 1.0 g·m⁻³ in flue gas and a gas velocity of 5 m·s⁻¹ demonstrated that this coated monolith catalyst is capable of resisting abrasion for 13 months without losing more than 8% of its initial activity. The result suggests the great potential of the coated monolith for application to de-NO_x of flue gases with low fly ash concentrations from, such as glass and ceramics manufacturing processes.     

Modification of the activated sludge model for chemical dosage

Full-scale experiments have been carried out to adapt the activated sludge model ASM2d to include the influence of metal dosage (Fe³⁺ and Al³⁺) for phosphorus removal. Phosphorus removal rates, nitrification rates, as well as pH and sludge settling performance, were evaluated as functions of the metal dosages. Furthermore, models relating certain parameters to the dosage of chemicals have been derived. Corresponding parameters in the ASM2d and the secondary settler models, included in the Benchmark Simulation Model No 1 (BSM1), have been modified to take the metal influence into consideration. Based on the effluent limits and penalty policy of China, an equivalent evaluation method was derived for the total cost assessment. A large number of 300-day steady-state and 14-day open-loop dynamic simulations were performed to demonstrate the difference in behavior between the original and the modified BSM1. The results show that 1) both in low and high mole concentrations, Fe³⁺ addition results in a higher phosphorus removal rate than Al³⁺; 2) the sludge settling velocity will increase due to the metal addition; 3) the respiration rate of the activated sludge is decreased more by the dosage of Al³⁺ than Fe³⁺; 4) the inhibition of Al³⁺ on the nitrification rate is stronger than that of Fe³⁺; 5) the total operating cost will reach the minimum point for smaller dosages of Fe³⁺, but always increase with Al³⁺ addition.     

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.     

Enhanced activation of peroxymonosulfate by CNT-TiO2 under UV-light assistance for efficient degradation of organic pollutants

CNT-TiO₂ composite is used to activate PMS under UV-light assistance. Superior performance is due to the enhanced electron-transfer ability of CNT. SO₄•⁻, •OH and ¹O₂ play key roles in the degradation of organic pollutants. In this work, a UV-light assisted peroxymonosulfate (PMS) activation system was constructed with the composite catalyst of multi-walled carbon nanotubes (CNT) - titanium dioxide (TiO₂). Under the UV light irradiation, the photoinduced electrons generated from TiO₂ could be continuously transferred to CNT for the activation of PMS to improve the catalytic performance of organic pollutant degradation. Meanwhile, the separation of photoinduced electron-hole pairs could enhance the photocatalysis efficiency. The electron spin resonance spectroscopy (EPR) and quenching experiments confirmed the generation of sulfate radical (SO₄•⁻), hydroxyl radical (•OH) and singlet oxygen (¹O₂) in the UV/PMS/20%CNT-TiO₂ system. Almost 100% phenol degradation was observed within 20 min UV-light irradiation. The kinetic reaction rate constant of the UV/PMS/20%CNT-TiO₂ system (0.18 min⁻¹) was 23.7 times higher than that of the PMS/Co₃O₄ system (0.0076 min⁻¹). This higher catalytic performance was ascribed to the introduction of photoinduced electrons, which could enhance the activation of PMS by the transfer of electrons in the UV/PMS/CNT-TiO₂ system.     

Hydrophilic/underwater superoleophobic graphene oxide membrane intercalated by TiO2 nanotubes for oil/water separation

GO/TiO₂ membrane was prepared by assembling GO nanosheets and TiO₂ nanotubes. The intercalation of TiO₂ nanotubes enlarged the space of GO interlayers and modified the surface morphology. Hydrophilic/underwater superoleophobic property of GO/TiO₂ membrane was obtained. Water permeability, hydrophilicity, oleophobicity and antifouling ability of GO-based membrane were all enhanced by intercalating TiO₂ nontubes. Membrane technology for oil/water separation has received increasing attention in recent years. In this study, the hydrophilic/underwater superoleophobic membrane with enhanced water permeability and antifouling ability were fabricated by synergistically assembling graphene oxide(GO) nanosheets and titanium dioxide (TiO₂) nanotubes for oil/water separation. GO/TiO₂ membrane exhibits hydrophilic and underwater superoleophobic properties with water contact angle of 62° and under water oil contact angle of 162.8°. GO/TiO₂ membrane shows greater water permeability with the water flux up to 531 L/(m²·h·bar), which was more than 5 times that of the pristine GO membrane. Moreover, GO/TiO₂membrane had excellent oil/water separation efficiency and anti-oil-fouling capability, as oil residual in filtrate after separation was below 5 mg/L and flux recovery ratios were over 80%.The results indicate that the intercalation of TiO₂ nanotubes into adjacent GO nanosheets enlarged the channel structure and modified surface topography of the obtained GO/TiO₂ membranes, which improved the hydrophilicity, permeability and anti-oil-fouling ability of the membranes, enlightening the great prospects of GO/TiO₂ membrane in oil-water treatment.     

Photocatalytic degradation of the acetaminophen by nanocrystal-engineered TiO2 thin film in batch and continuous system

• Photocatalytic activity was improved in TiO₂ thin film by rapid thermal annealing. • Photoreactor was designed for TiO₂ thin film. • Considerable reusability and durability of prepared photocatalysts were studied. Un-biodegradable pharmaceuticals are one of the major growing threats in the wastewaters. In the current study, TiO₂ thin film photocatalysts were designed by nanocrystal engineering and fabricated for degradation of the acetaminophen (ACE) in a photocatalytic reaction under UV light irradiation in batch and continuous systems. The photocatalyst was prepared by sputtering and then engineered by thermal treatment (annealing at 300℃ (T300) and 650℃ (T650)). The annealing effects on the crystallinity and photocatalytic activity of the TiO₂ film were completely studied; it was found that annealing at higher temperatures increases the surface roughness and grain size which are favorable for photocatalytic activity due to the reduction in the recombination rate of photo-generated electron-hole pairs. For the continuous system, a flat plate reactor (FPR) was designed and manufactured. The photocatalytic performance was decreased with the increase of flow rate because the higher flow rate caused to form the thicker film of the liquid in the reactor and reduced the UV light received by photocatalyst. The reusability and durability of the samples after 6 h of photocatalytic reaction showed promising performance for the T650 sample (annealed samples in higher temperatures).     

Comparing the adsorption behaviors of Cd,Cu and Pb from water onto Fe-Mn binary oxide,MnO2 and FeOOH

The adsorption potential of FMBO, FeOOH, MnO₂ for the removal of Cd²⁺, Cu²⁺ and Pb²⁺ in aqueous systems was investigated in this study. Comparing to FMBO and FeOOH, MnO₂ offered a much higher removal capacity towards the three metal ions. The maximal adsorption capacity of MnO₂ for Cd²⁺, Cu²⁺ and Pb²⁺ were 1.23, 2.25 and 2.60 mmol·g^-1, respectively. And that for FMBO were 0.37, 1.13, and 1.18 mmol·g^-1 and for FeOOH were 0.11, 0.86 and 0.48 mmol·g^-1, respectively. The adsorption behaviors of the three metal ions on the three adsorbents were all significantly affected by pH values and heavy metal removal efficiency increased with pH increased. The Langmuir and Freundlich adsorption models were used to describe the adsorption equilibrium of the three metal ions onto the three adsorbents. Results showed that the adsorption equilibrium data fitted well to Langmuir isotherm and this indicated that adsorption of metal ions occurred on the three metal oxides adsorbents limited to the formation of a monolayer. More negative charged of MnO₂ surface than that of FMBO and FeOOH could be ascribed by lower pH_iep of MnO₂ than that of FMBO and FeOOH and this could contribute to more binding sites on MnO₂ surface than that of FMBO and FeOOH. The higher metal ions uptake by MnO₂ than FMBO and FeOOH could be well explained by the surface charge mechanism.     

UV-LED/P25-based photocatalysis for effective degradation of isothiazolone biocide

• UV-LED with shorter wavelength was beneficial for photocatalytic degradation. • SRNOM dramatically inhibit the degradation. • ·OH acts as the active radical in photocatalytic degradation. • Degradation mainly undergoes oxidation, hydrolysis and chain growth reactions. In this work, LED-based photocatalysis using mixed rutile and anatase phase TiO₂ (P25) as the photocatalyst could effectively remove 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT) and methylisothiazolone (MIT) simultaneously, with removal efficiencies above 80% within 20 min. The photocatalytic degradation of both CMIT and MIT could be modeled using a pseudo-first-order rate equation. The photocatalytic degradation rates of CMIT and MIT under LED280 illumination were higher than under LED310 or LED360 illumination. At concentrations below 100 mg/L, the degradation rate of CMIT and MIT under LED illumination significantly increased with increasing catalyst dosage. Additionally, the effects of the chloride ion concentration, alkalinity and dissolved organic matter on the photocatalytic degradation reaction were also investigated. The ·OH free radicals were determined to play the primary role in the photocatalytic degradation reaction, with a degradation contribution of >95%. The photocatalytic degradation of CMIT and MIT mainly occurred via oxidation, hydrolysis, and chain growth reactions. Finally, the possible photocatalytic degradation pathways of CMIT and MIT over LED/P25 are proposed.     

Translocation and biotoxicity of metal (oxide) nanoparticles in the wetland-plant system

• Aquatic plants are more likely to absorb TiO₂ NPs that are beneficial to them. • Ag NPs inhibited the growth of aquatic plants under both 5- and 60-day exposure. • CeO₂ NPs had positive/negative impact on plant in 5/60-day exposure, respectively. • TiO₂ NPs presence could enhance the photosynthesis and increase the plant biomass. • The ENPs changed plant activity, which resulted in changes of wetland performance. Engineered nanoparticles (ENPs) threaten the environment through wastewater discharging. Generally, constructed wetlands (CWs) are efficient methods for ENPs removal. However, the biotoxicity of ENPs on plants in CWs is unclear. Here, we investigated the distribution and bio-impacts of different ENPs (Ag NPs, TiO₂ NPs, and CeO₂ NPs) in plants under 5- and 60-day exposure to 1 and 50 mg/L concentrations. Results showed that ENPs appeared in the vascular bundle and mesophyll cell space, which induced the variation in antioxidase activities (e.g., superoxide dismutase [SOD], peroxidase [POD], and catalase [CAT] activities) as well as overproduction of malondialdehyde (MDA). Additionally, Ag NPs inhibited photosynthesis rate and root activity during two exposure phases. CeO₂ NPs had positive and negative impacts on plants in 5- and 60-day exposure, respectively. Inversely, TiO₂ NPs enhanced photosynthesis and root activity under 60-day exposure. Finally, the contents of the C, N, and P elements in plants fluctuated in response to ENPs stress. All results have a positive correlation with the wetland performance under ENPs exposure except for TiO₂ NPs treatment. Overall, our study systematically reveals aquatic plants' responses to ENPs and provides a reference for building ecological treatment systems to purify wastewater containing ENPs.     

Ce(x)Mn/TiO2-y催化剂低温NH3-SCR脱硝性能

以锐钛矿TiO₂(P25)为载体采用原位生长法负载锰氧化物制备了Mn/TiO₂催化剂,再以等体积浸渍-煅烧法对该催化剂掺杂氧化铈制备Ce(x)Mn/TiO₂-y催化剂用以烟气低温SCR脱硝.在固定锰负载量(质量分数为8%)的基础上,考察了铈掺杂量(铈锰摩尔比)、煅烧温度对催化剂SCR脱硝性能的影响.采用TEM、BET、XRD和XPS等手段表征了催化剂的理化结构特性.结果发现,当Ce/Mn的摩尔比例为1.0,煅烧温度为300℃时,Ce(1.0)Mn/TiO₂-300催化剂在150—300℃温度范围内、10500—27000 h^-1的空速范围内,能够保持90%以上的NO转化率.理化性能分析结果表明,煅烧温度对催化剂的微观形貌影响显著,随着煅烧温度的升高,Ce(1.0)Mn/TiO₂-500催化剂活性物种颗粒集聚明显、比表面积降低,且锰氧化物价态分布偏向于低价态;铈的掺杂有助于Ce(1.0)Mn/TiO₂-300催化剂活性物种在载体表面的均匀分散,可以促进产生更多的Mn4+物种和更多的吸附氧,有利于催化剂低温SCR脱硝性能的提升.     

Removal of fluoride from water using titanium-based adsorbents

Three adsorbents including TiO₂, Ti-Ce, and Ti-La hybrid oxides were prepared to remove fluoride from aqueous solution. The Ti-Ce and Ti-La hybrid adsorbents obtained by the hydrolysis-precipitation method had much higher sorption capacity for fluoride than the TiO₂ adsorbent prepared through hydrolysis. Rare earth (Ce and La) oxides and TiO₂ exhibited a synergistic effect in the hybrid adsorbents for fluoride sorption. The sorption equilibrium of fluoride on the three adsorbents was achieved within 4 h, and the pseudo-second-order model described the sorption kinetics well. The sorption isotherms fitted the Langmuir model well, and the adsorption capacities of fluoride on the Ti-Ce and Ti-La adsorbents were about 9.6 and 15.1 mg·g^-1, respectively, at the equilibrium fluoride concentration of 1.0 mg·L^-1, much higher than the 1.7 mg·g^-1 on the TiO₂. The sorption capacities of fluoride on the three adsorbents decreased significantly when the solution pH increased from 3 to 9.5. The electrostatic interaction played an important role in fluoride removal by the three adsorbents, and Fourier transform infrared (FTIR) analysis indicated that the hydroxyl groups on the adsorbent surface were involved in fluoride adsorption.     

Investigation of the effects of humic acid and H 2 O 2 on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s⁻¹, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Response of bioaerosol cells to photocatalytic inactivation with ZnO and TiO2 impregnated onto Perlite and Poraver carriers

•ZnO/Perlite inactivated 72% of bioaerosols in continuous gas phase. •TiO₂ triggered the highest level of cytotoxicity with 95% dead cells onto Poraver. •Inactivation mechanism occurred by membrane damage, morphological changes and lysis. •ZnO/Poraver showed null inactivation of bioaerosols. •Catalysts losses at the outlet of the photoreactor for all systems were negligible. Bioaerosols are airborne microorganisms that cause infectious sickness, respiratory and chronic health issues. They have become a latent threat, particularly in indoor environment. Photocatalysis is a promising process to inactivate completely bioaerosols from air. However, in systems treating a continuous air flow, catalysts can be partially lost in the gaseous effluent. To avoid such phenomenon, supporting materials can be used to fix catalysts. In the present work, four photocatalytic systems using Perlite or Poraver glass beads impregnated with ZnO or TiO₂ were tested. The inactivation mechanism of bioaerosols and the cytotoxic effect of the catalysts to bioaerosols were studied. The plug flow photocatalytic reactor treated a bioaerosol flow of 460×1 0⁶ cells/m³_air with a residence time of 5.7 s. Flow Cytometry (FC) was used to quantify and characterize bioaerosols in terms of dead, injured and live cells. The most efficient system was ZnO/Perlite with 72% inactivation of bioaerosols, maintaining such inactivation during 7.5 h due to the higher water retention capacity of Perlite (2.8 mL/g_Perlite) in comparison with Poraver (1.5 mL/g_Perlite). However, a global balance showed that TiO₂/Poraver system triggered the highest level of cytotoxicity to bioaerosols retained on the support after 96 h with 95% of dead cells. SEM and FC analyses showed that the mechanism of inactivation with ZnO was based on membrane damage, morphological cell changes and cell lysis; whereas only membrane damage and cell lysis were involved with TiO₂. Overall, results highlighted that photocatalytic technologies can completely inactivate bioaerosols in indoor environments.     

Identification and ecotoxicity assessment of intermediates generated during the degradation of clofibric acid by advanced oxidation processes

The aim of this study was to identify the intermediates in clofibric acid degradation under various advanced oxidation processes, namely ultraviolet (UV), UV/H₂O₂, vacuum ultraviolet (VUV), VUV/H₂O₂, and solar/TiO₂ processes, as well as to assess the toxicity of these intermediates. Eleven intermediates have been detected by gas chromatography-mass spectrometer, most of which were reported for the first time to our best knowledge. Combining the evolution of the dissolved organic carbon, Cl^- and specific ultraviolet absorption at 254 nm, it could be deduced that cleavage of aromatic ring followed by dechlorination was the mechanism in solar/TiO₂ process, while dechlorination happened first and accumulation of aromatic intermediates occurred in the other processes. Different transformation pathways were proposed for UV-, VUV-assisted and solar/TiO₂ processes, respectively. The acute toxicity was evaluated by means of Photobacterium phosphoreum T₃ spp. bioassay. It was believed that aromatic intermediates increased the toxicity and the ring-opening pathway in solar/TiO₂ process could relieve the toxicity.