Assessing combined toxic effects of tetracycline and P25 titanium dioxide nanoparticles using Allium cepa bioassay

• UVA pre-irradiation to TiO₂ NPs enhanced its toxicity toward plant A. cepa. • UVA TiO₂ NPs increased intracellular ROS, resulting in more cell damage. • Cell death enhanced cell permeability and increased uptake of NPs. • Being highly toxic (EC₅₀ = 0.097 µmol/L), TC did not increase ROS generation. • Even at a low dose, TC enhanced the toxic potential of TiO₂ NPs significantly. Usage of titanium dioxide nanoparticles (TiO₂ NPs) and tetracycline (TC) has increased significantly in the present era. This leads to their release and accumulation in the environment. Both the compounds, individually, can have adverse toxic effects on the plants. Their binary mixtures can increase this degree of damage. The present study aimed to evaluate the toxicity of both the contaminants in individual and binary mixtures in Allium cepa. Further, the toxicity of TiO₂ NPs upon UVA pre-irradiation was also measured. Results showed that UVA pre-irradiated NPs (UVA-TiO₂ NPs) had a significant decrease in cell viability than their non-irradiated counterparts (NI-TiO₂), denoting an increase in photocatalytic activity upon UVA pre-irradiation. Very low concentrations of TC (EC₁₀ = 0.016 µmol/L) mixed with TiO₂ NPs significantly increased the toxicity for both UVA-TiO₂ and NI-TiO₂ NPs. Intracellular ROS generation was significantly high for UVA-TiO₂ NPs. However, TC did not have any effects on ROS production. Both the compounds exhibited genotoxic potential in A. cepa. Different chromosomal abnormalities like anaphase bridges, telophase bridges, laggard chromosomes, binucleate cells, etc. were observed. The binary mixture of UVA-TiO₂ NPs and TC showed the highest chromosomal aberrations (64.0%±1.26%) than the mixture with NI-TiO₂ or the individual contaminants. This decreased significantly after recovery (46.8%±1.92%), denoting the self-repair processes. This study proved that UVA-TiO₂ NPs were more toxic and could be enhanced further when mixed with a sub-lethal concentration of TC. This work will help to assess the risk of both compounds in the environment.     

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.     

Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied. • DCM was completely eliminated at 350℃ under 1 vol.% humidity. • Anatase (001) was the key for disproportionation. • A competitive oxidation route co-existed with disproportionation. • Disproportionation was favored at low temperature. Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.     

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.     

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).     

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.     

Removal and recovery of toxic nanosized Cerium Oxide using eco-friendly Iron Oxide Nanoparticles

• Eco-friendly IONPs were synthesized through solvothermal method. • IONPs show very high removal efficiency for CeO₂ NPs i.e. 688 mg/g. • Removal was >90% in all synthetic and real water samples. • >80% recovery of CeO₂ NPs through sonication confirms reusability of IONPs. Increasing applications of metal oxide nanoparticles and their release in the natural environment is a serious concern due to their toxic nature. Therefore, it is essential to have eco-friendly solutions for the remediation of toxic metal oxides in an aqueous environment. In the present study, eco-friendly Iron Oxide Nanoparticles (IONPs) are synthesized using solvothermal technique and successfully characterized using scanning and transmission electron microscopy (SEM and TEM respectively) and powder X-Ray diffraction (PXRD). These IONPs were further utilized for the remediation of toxic metal oxide nanoparticle, i.e., CeO₂. Sorption experiments were also performed in complex aqueous solutions and real water samples to check its applicability in the natural environment. Reusability study was performed to show cost-effectiveness. Results show that these 200 nm-sized spherical IONPs, as revealed by SEM and TEM analysis, were magnetite (Fe₃O₄) and contained short-range crystallinity as confirmed from XRD spectra. Sorption experiments show that the composite follows the pseudo-second-order kinetic model. Further R²>0.99 for Langmuir sorption isotherm suggests chemisorption as probable removal mechanism with monolayer sorption of CeO₂ NPs on IONP. More than 80% recovery of adsorbed CeO₂ NPs through ultrasonication and magnetic separation of reaction precipitate confirms reusability of IONPs. Obtained removal % of CeO₂ in various synthetic and real water samples was>90% signifying that IONPs are candidate adsorbent for the removal and recovery of toxic metal oxide nanoparticles from contaminated environmental water samples.     

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.     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.     

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.     

Application and mechanism of polysaccharide extracted from Enteromorpha to remove nano-ZnO and humic acid in coagulation process

Green source Ep was extracted from marine alga waste. The molecule model structure of Ep was studied and constructed. PAC-Ep coagulation system improves the efficiency of removal efficiency. Synergistic effects between NPs and HA make a big difference to enhance efficiency. Mechanism is charge neutralization, hydrogen bonding and adsorbing-complexing Enteromorpha polysaccharide (Ep) extracted from alga a novel green coagulant aid for nanoparticles (NPs) and heavy metal ions removal and the structure of EP was intensively studied in this study. The integration of Ep with polyaluminum chloride (PAC-Ep) coagulants exhibited higher coagulation performance than that of the polyaluminum chloride (PAC) because of the negatively charged NPs suspension and humic aid (HA) solution. Significant high removal efficiencies of dissolved organic matter (94.1%), turbidity (99.3%) and Zn ions (69.3%) were achieved by the PAC-Ep coagulants. The dual-coagulation properties of PAC-Ep for different pollutants was based on multiple mechanisms, including (i) Al³⁺ charge neutralization; (ii) hydroxy aluminum hydroxyl bridging formed polynuclearhydroxy complexes bridge and sweep colloidal particles; (iii) adsorption and bridging of Ep chain for the NPs and heavy metal ions. Results indicated that the destabilization of colloid was induced by the coexisting HA and higher removal was achieved as ions adsorption was enhance in the presence of HA complexation. On the basis of that, the extraction of polysaccharide is a promising candidate for its high coagulation performance in water treatment.     

Influence of extracellular polymeric substances from activated sludge on the aggregation kinetics of silver and silver sulfide nanoparticles

• The NPs aggregation in the electrolyte solution is consistent with the DLVO theory. • In NaNO₃ and low Ca(NO₃)₂, EPS alleviates the NPs aggregation by steric repulsion. • In high Ca(NO₃)₂, EPS accelerates the NPs aggregation by exopolysaccharide bridging. • Ag₂S NPs have stronger stability compared with Cit-Ag NPs in aqueous systems. Extracellular polymeric substances (EPS) in activated sludge from wastewater treatment plants (WWTPs) could affect interactions between nanoparticles and alter their migration behavior. The influence mechanisms of silver nanoparticles (Ag NPs) and silver sulfide nanoparticles (Ag₂S NPs) aggregated by active EPS sludge were studied in monovalent or divalent cation solutions. The aggregation behaviors of the NPs without EPS followed the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The counterions aggravated the aggregation of both NPs, and the divalent cation had a strong neutralizing effect due to the decrease in electrostatic repulsive force. Through extended DLVO (EDLVO) model analysis, in NaNO₃ and low-concentration Ca(NO₃)₂ (<10 mmol/L) solutions, EPS could alleviate the aggregation behaviors of Cit-Ag NPs and Ag₂S NPs due to the enhancement of steric repulsive forces. At high concentrations of Ca(NO₃)₂ (10‒100 mmol/L), exopolysaccharide macromolecules could promote the aggregation of Cit-Ag NPs and Ag₂S NPs by interparticle bridging. As the final transformation form of Ag NPs in water environments, Ag₂S NPs had better stability, possibly due to their small van der Waals forces and their strong steric repulsive forces. It is essential to elucidate the surface mechanisms between EPS and NPs to understand the different fates of metal-based and metal-sulfide NPs in WWTP systems.     

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.     

Relations between indoor and outdoor PM2.5 and constituent concentrations

Factors impacting indoor-outdoor relations are introduced. Sulfate seems a fine tracer for other non-volatile species. Particulate nitrate and ammonium desorb during outdoor-to-indoor transport. OC load increases during the transport due to sorption of indoor SVOCs. Outdoor PM_2.5 influences both the concentration and composition of indoor PM_2.5. People spend over 80% of their time indoors. Therefore, to assess possible health effects of PM_2.5 it is important to accurately characterize indoor PM_2.5 concentrations and composition. Controlling indoor PM_2.5 concentration is presently more feasible and economic than decreasing outdoor PM_2.5 concentration. This study reviews modeling and measurements that address relationships between indoor and outdoor PM_2.5 and the corresponding constituent concentrations. The key factors in the models are indoor-outdoor air exchange rate, particle penetration, and deposition. We compiled studies that report I/O ratios of PM_2.5 and typical constituents (sulfate (SO₄^2-), nitrate (NO₃^-), ammonium (NH₄⁺), elemental carbon (EC), and organic carbon (OC), iron (Fe), copper (Cu), and manganese (Mn)). From these studies we conclude that: 1) sulfate might be a reasonable tracer of non-volatile species (EC, Fe, Cu, and Mn) and PM_2.5 itself; 2) particulate nitrate and ammonium generally desorb to gaseous HNO₃ and NH₃ when they enter indoors, unless, as seldom happens, they have strong indoor sources; 3) indoor-originating semi-volatile organic compounds sorb on indoor PM_2.5, thereby increasing the PM_2.5 OC load. We suggest further studies on indoor-outdoor relationships of PM_2.5 and constituents so as to help develop standards for healthy buildings.     

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.     

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.     

Mechanistic insights into the selective photocatalytic degradation of dyes over TiO2/ZSM-11

● TiO₂/ZSM-11 was prepared by a facile solid state dispersion method. ● Mechanism for photocatalytic degradation of dyes was investigated. ● Both experimental and MD simulations were conducted. ● Chemisorption instead of electrostatic interaction played a critical role. Photocatalytic degradation is a promising way to eliminate dye contaminants. In this work, a series of TiO₂/ZSM-11 (TZ) nanocomposites were prepared using a facile solid state dispersion method. Methyl orange (MO), methylene blue (MB), and rhodamine B (RhB) were intentionally chosen as target substrates in the photocatalytic degradation reactions. Compared to pristine TiO₂, negative effect was observed on MO degradation while promoted kinetics were collected on MB and RhB over TZ composites. Moreover, a much higher photocatalytic rate was interestingly achieved on RhB than MB, which indicated that a new factor has to be included other than the widely accepted electrostatic interaction mechanism to fully understand the selective photodegradation reactions. Systematic characterizations showed that TiO₂ and ZSM-11 physically mixed and maintained both the whole framework and local structure without chemical interaction. The different trends observed in surface area and the photo-absorption ability of TZ composites with reaction performance further excluded both as the promotion mechanism. Instead, adsorption energies predicted by molecular dynamics simulations suggested that differences in the adsorption strength played a critical role. This work provided a deep mechanistic understanding of the selective photocatalytic degradation of dyes reactions, which helps to rationally design highly efficient photocatalysts.     

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.     

Optimization of the O3/H2O2 process with response surface methodology for pretreatment of mother liquor of gas field wastewater

• Real ML-GFW with high salinity and high organics was degraded by O₃/H₂O₂ process. • Successful optimization of operation conditions was attained using RSM based on CCD. • Single-factor experiments in advance ensured optimal experimental conditions. • The satisfactory removal efficiency of TOC was achieved in spite of high salinity. • The initial pH plays the most significant role in the degradation of ML-GFW. The present study reports the use of the O₃/H₂O₂ process in the pretreatment of the mother liquor of gas field wastewater (ML-GFW), obtained from the multi-effect distillation treatment of the gas field wastewater. The range of optimal operation conditions was obtained by single-factor experiments. Response surface methodology (RSM) based on the central composite design (CCD) was used for the optimization procedure. A regression model with Total organic carbon (TOC) removal efficiency as the response value was established (R² = 0.9865). The three key factors were arranged according to their significance as: pH>H₂O₂ dosage>ozone flow rate. The model predicted that the best operation conditions could be obtained at a pH of 10.9, an ozone flow rate of 0.8 L/min, and H₂O₂ dosage of 6.2 mL. The dosing ratio of ozone was calculated to be 9.84 mg O₃/mg TOC. The maximum removal efficiency predicted was 75.9%, while the measured value was 72.3%. The relative deviation was found to be in an acceptable range. The ozone utilization and free radical quenching experiments showed that the addition of H₂O₂ promoted the decomposition of ozone to produce hydroxyl radicals (·OH). This also improved the ozone utilization efficiency. Gas chromatography-mass spectrometry (GC-MS) analysis showed that most of the organic matters in ML-GFW were degraded, while some residuals needed further treatment. This study provided the data and the necessary technical supports for further research on the treatment of ML-GFW.