Insight into Fe-O-Bi electron migration channel in MIL-53(Fe)/Bi4O5I2 Z-scheme heterojunction for efficient photocatalytic decontamination.

Building a heterojunction is a fascinating option to guarantee sufficient carrier separation and transfer efficiency, but the mechanism of charge migration at the heterojunction interface has not been thoroughly studied. Herein, MIL-53(Fe)/Bi4O5I2 photocatalyst with a Z-scheme heterojunction structure is constructed, which achieves efficient photocatalytic decontamination under solar light. Driven by the newly-built internal electric field (IEF), the formation of Fe-O-Bi electron migration channel allows for rapid separation and transfer of charge carriers at the heterojunction interface, confirmed by the material characterization and density functional theory (DFT) calculation. The narrower band gap and improved visible light response also contribute to the enhanced photocatalytic activity of composite materials. With levofloxacin as the target pollutant, the optimal MIL-53(Fe)/Bi4O5I2 achieves complete removal of pollutant within 150 min, the photocatalysis rate of which is ca. 4.4 and 26.0 times that of pure Bi4O5I2 and MIL-53(Fe), respectively. Simultaneously, the optimal composite material exhibits satisfactory photodegradation of seven fluoroquinolones, and the photocatalysis rates are as follows: lomefloxacin > ciprofloxacin > enrofloxacin > norfloxacin > pefloxacin > levofloxacin > marbofloxacin. DFT calculations reveal a positive relationship between degradation rate and Fukui index (ƒ0) of main carbon atoms in seven fluoroquinolones. This study sheds light on the existence of electron migration channels at Z-scheme heterojunction interface to ensure sufficient photoinduced carrier transfer, and reveals the influence of pollutant structure on photolysis rate.

Ceftriaxone sodium degradation by carbon quantum dots (CQDs)-decorated C-doped α-Bi2O3 nanorods.

A novel carbon quantum dots decorated C-doped α-Bi2O3 photocatalyst (CBO/CQDs) was synthesized by solvothermal method. The synergistic effect of adsorption and photocatalysis highly improved contaminants removal efficiencies. The ceftriaxone sodium degradation rate constant (k) of CBO/CQDs was 11.4 and 3.2 times that of pure α-Bi2O3 and C-doped α-Bi2O3, respectively. The interstitial carbon doping generated localized states above the valence band, which enhanced the utilization of visible light and facilitated the separation of photogenerated electrons and holes; the loading of CQDs improved the charge carrier separation and extended the visible light response; the reduced particle size of CBO/CQDs accelerated the migration of photogenerated carriers. The •O2 - and h+ were identified as the dominant reactive species in ceftriaxone sodium degradation, and the key role of •O2 - was further investigated by NBT transformation experiments. The Fukui index was applied to ascertain the molecular bonds of ceftriaxone sodium susceptible to radical attack, and intermediates analysis was conducted to explore the possible degradation pathways. The toxicity evaluation revealed that some degradation intermediates possessed high toxicity, thus the contaminants require sufficient mineralization to ensure safe discharge. The present study makes new insights into synchronous carbon dopping and CQDs decoration on modification of α-Bi2O3, which provides references for future studies.

Semiconducting mineral induced photochemical conversion of PAHs in aquatic environment: Mechanism study and fate prediction.

Semiconducting minerals (such as iron sulfides) are highly abundant in surface water, but their influences on the natural photochemical process of contaminants are still unknown. By simulating the natural water environment under solar irradiation, this work comprehensively investigated the photochemical processes of anthracene (a typical Polycyclic Aromatic Hydrocarbons) in both freshwater and seawater. The results show that the natural pyrite (NP) significantly promotes the degradation of anthracene under solar illumination via 1) NP induced photocatalytic degradation of anthracene, and 2) Fenton reaction due to the NP induced photocatalytic generation of H2O2. The material characterization and theoretical calculation reveal that the natural impurity in NP enlarges its band gap, which limits the utilization of solar spectra to shorter wavelength. The contribution of generated reactive intermediates on anthracene degradation follows the order of 1O2 >OH > O2- in freshwater and O2- >1O2 >OH in seawater. The photochemically generated H2O2 is a vital source for OH generation (from Fenton reaction). The steady-state concentration of OH, 1O2 and O2- in freshwater were monitored as 3.0 × 10-15 M, 1.1 × 10-13 M, and 4.5 × 10-14 M, respectively. However, the OH concentration in seawater can be negligible due to the quenching effects by halides, and the 1O2 and O2- concentrations are higher than that in freshwater. An anthracene degradation kinetic model was built based on the experimentally determined reactive intermediates concentration and its second order rate constant with anthracene. Moreover, the anthracene degradation pathway was proposed based on intermediates analysis and DFT calculation, and its toxicity evolution during the photochemical process was assessed by quantitative structure-activity relationship (QSAR) based prediction. This finding suggests that the natural semiconducting minerals can affect the fate and environmental risks of contaminants in natural water.

Elevated nitrate promoted photodegradation of PAHs in aqueous phase: Implications for the increased nutrient discharge.

Polycyclic aromatic hydrocarbons (PAHs) are frequently released in aqueous phase by oil spill or from other sources, and photochemical oxidation is one of their major weathering processes. In this study, the photochemical behavior of phenanthrene (PHE, as a representative PAH) were studied and the effects of nitrogenous compounds were evaluated. The results showed that nitrate was an effective photosensitizer for improving the photodegradation of PHE, but the promoting effect was less effective in seawater due to the presence of halogen ions; the ammonia played a negligible role on PHE degradation. The photochemical ionization was a key process for PHE degradation, it can be retarded due to the quenching of triplet excited state by dissolved oxygen, and the inhibition was most prominent in fresh water. The presence of nitrate increased the steady state concentration of •OH from 2.08 × 10-15 M to 1.04 × 10-14 M in fresh water, and from 1.5 × 10-16 M to 2.08 × 10-15 M in seawater. The secondary-order reaction rate constant between PHE and •OH (k•OH,PHE) was determined as 5.70 × 109 M-1 s-1. Similar trend was observed for 1O2. The contribution of •OH to PHE removal was more prominent in fresh water than in seawater due to the quenching effects of halogen, and the increasing of nitrate enlarged the contribution of •OH. Two possible PHE degradation pathways were proposed based on GC-MS analysis and DFT calculation. The Quantitative Structure-activity Relationship (QSAR) evaluation showed that some degradation intermediates were more toxic than PHE, but the total environmental risk was still diminished due to the low percentage of toxic intermediates. This study provided theoretical and experimental insights into the influence of nitrogenous compounds on the photodegradation of PHAs in water environment.

Enhanced removal of humic substances in effluent organic matter from a leachate treatment system via biological upgradation of molecular structure.

Biological upgradation (BU) process was proposed, with the goal of converting the molecular structure, for improving the coagulation effect on humic substances (HS) in effluent organic matter from the membrane bioreactor of a leachate treatment system. Enhancement of coagulation effect was observed with the improvement of chemical oxygen demand and HS removal efficiency from 45.5% and 56.5% to 80.0% and 92.6% (Fe dosage was 400 mg·L-1), respectively, which was approximately 30-40% higher than the other available researches. Variations in molecular weight (MW) and carboxyl contents of fulvic acid (FA) and humic acid (HA) were analysed by size exclusion chromatography coupled with dissolved organic carbon detection, potentiometric titration and Fourier transform infrared spectroscopy. The obtained results indicated that BU process led to the growth of MW of HS, of which the larger MW (1650 Da) FA and HA raised from 19.07 and 0.34 mgC·L-1 to 71.67 and 1.58 mgC·L-1, respectively, as well as increases in the carboxyl contents of FA and HA from 6.70 and 6.28 meq·gC-1 to 11.84 and 8.71 meq·gC-1, respectively. Because of this, a stronger binding effect between Fe and HS might be formed that improved the coagulation effect.

Highly efficient AgBr/h-MoO3 with charge separation tuning for photocatalytic degradation of trimethoprim: Mechanism insight and toxicity assessment.

A highly solar active AgBr/h-MoO3 composite was constructed by a facile precipitation method, and the charge separation tuning was achieved by photoreduction of AgBr. The photoreduced Ag0 on AgBr/h-MoO3 acted as charge transfer bridge to form Z-scheme heterostructure, while the high degree of Ag reduction converted the material into type-II heterostructure. The synthesized optimal material promoted charge separation and visible light activity due to the incorporation of highly solar active AgBr, which showed ca. 2 times activity on trimethoprim (TMP) degradation than h-MoO3. The contribution of reactive species on TMP degradation followed the order of O2- >1O2 > h+, which agree well with the proposed charge separation mechanism. The photocatalytic degradation mechanism of TMP was proposed based on the radical quenching, intermediate analysis and DFT calculation. The toxicity analysis based on QSAR calculation showed that part of the degradation intermediates are more toxic than TMP, thus sufficient mineralization are required to eliminate the potential risks of treated water. Moreover, the material showed high stability and activity after four reusing cycles, and it is applicable to treat contaminants in various water matrix. This work is expected to provide new insight into the charge separation tuning mechanism for the AgX based heterojunction, and rational design of highly efficient photocatalysts for organic contaminants degradation by solar irradiation.

Surface modification of BiOBr/TiO2 by reduced AgBr for solar-driven PAHs degradation: Mechanism insight and application assessment.

A novel solar active AgBr/BiOBr/TiO2 catalyst was synthesized by a facile coprecipitation method for solar-driven water remediation. The synthesized material composed of flower-like TiO2 nanoparticles loaded on BiOBr nanosheets and with homogeneous surface distributed Ag/AgBr nanoparticles. The internal electric field between BiOBr/TiO2 heterojunction greatly facilitated the charge carrier migration; the introduction of narrow band gap semiconductors (AgBr and BiOBr) promoted the visible light adsorption; and the Ag/AgBr nanoparticles acted as photosensitizer to further improve the light utilization. The new material showed 7.6- and 4.0-times activity of pure TiO2 and BiOBr under solar light, and the contribution of reactive species on anthracene degradation followed the order of h+ >O2•-> •OH. The degradation mechanism and pathway were proposed based on intermediates analysis and DFT calculation. The QSAR analysis revealed that the environmental risks of contaminants were greatly reduced during the photocatalysis process but some intermediates were still toxic. The high photocatalytic activity, stability and adaptability all indicated that this new material owns great application potential for cost-effective photocatalytic remediation of persistent organic contaminants under solar light.

Highly active WO3@anatase-SiO2 aerogel for solar-light-driven phenanthrene degradation: Mechanism insight and toxicity assessment.

The global energy crisis and water pollution drive the researchers to develop highly effective and less energy intensive water purification technologies. In this study, a highly active WO3@TiO2-SiO2 nanocomposite was synthesized and used for photocatalytic degradation of persistent organic pollutants under simulated solar light. The optimum WO3@TiO2-SiO2 prepared with 2 wt% WO3 loading and calcination at 800 °C exhibited higher photocatalytic activity, as the rate constant (k1) for phenanthrene degradation was ∼7.1 times of that for the commercial TiO2 (P25). The extremely large specific surface area (>400 m2/g) of WO3@TiO2-SiO2 afforded it with enlarged pollutants adsorption performance and abundant active surface sites. The heterojunction of anatase with SiO2 as well as loading of WO3 decreased the band gap energy (Eg) of TiO2, which extended the utilization spectrum of TiO2 to visible region. Formation of Ti-O-Si band indicated the excess charges can cause Brønsted acidity due to the absorption of protons to compensate the charges. Moreover, the migration of photo-excited electrons from the conduction band of anatase to WO3 and holes in the opposite direction restrained the electron-hole recombination. The photocatalytic degradation mechanism and pathway for phenanthrene degradation were proposed based on experimental analysis and density functional theory (DFT) calculation, and the toxicities of the degradation intermediates were evaluated by quantitative structure-activity relationship (QSAR) analysis. WO3@TiO2-SiO2 also showed good separation (settling) performance and high stability. Our work is expected to offer new insight into the photocatalytic mechanism for WO3, TiO2 and SiO2 based heterojunctions, and rational design and synthesis of highly efficient photocatalysts for environmental application.

Removal and transformation of effluent organic matter (EfOM) in biotreated textile wastewater by GAC/O3 pre-oxidation and enhanced coagulation.

GAC/O3 (ozonation in the presence of granular activated carbon) combined with enhanced coagulation was employed to process biotreated textile wastewater for possible reuse. The doses of ozone, GAC and coagulant were the variables studied for optimization. The effects of different treatment processes on effluent organic matter (EfOM) characteristics, including biodegradability, hydrophobic and hydrophilic nature, and apparent molecular weight (AMW) distribution were also investigated. Compared with ozonation, GAC/O3 not only presented a higher pre-oxidation efficiency, but also improved the treatability of hydrophobic and high molecular weight compounds by enhanced coagulation. After treatment by GAC/O3 pre-oxidation (0.6 mg O3 x mg(-1) COD and 20 g x L(-1) GAC) and enhanced coagulation (25 mg x L(-1) Al3+ at pH 5.5), the removal efficiencies of chemical oxygen demand (COD), dissolved organic carbon (DOC) and colour were higher than those for coagulation alone by 17.3%, 12.0% and 25.6%, respectively. Residual organic matter consisted mainly of hydrophobic acids and hydrophilic compounds of AMW < 1 kDa, which were colourless and of limited biological availability. The combination of GAC/O3 and enhanced coagulation was proved to be a simple and effective treatment strategy for removing EfOM from biotreated textile wastewater.

[Study on removal effect of different organic fractions from bio-treated effluent of dye wastewater by UV/H2O2 process].

The pretreatment of bio-treated effluent of dye wastewater by UV/H2O2 process was studied. The influencing factors, such as H2O2 dosage, reaction time and pH values were evaluated for the removal efficiency of UV254, ADMI7.6, DOC and DOC of dye wastewater by UV/H2O2 process. The experimental results showed that,the optimal conditions determined were as follows: initial pH 7.4-8.1, H2O2 dosage 4.5 mmol x L(-1) and UV irradiation time of 50 min. Under the optimal conditions, UV254, ADMI7.6, DOC and COD removal rate could reach 77%, 94%, 40% and 69%. Removal effects of four different DOM fractions, hydrophobic acids, non-acid hydrophobics, tasnsphilics and hydrophilics separated by XAD-8 and XAD-4 resins. The experimental results show that: hydrophobic material was the main substance causing color, when it was characterized by ADMI7.6, the proportion could reach 92%, of which 53% was non-acid hydrophobics. It indicated that removal efficiencies of tasnsphilics, hydrophobic acids and non-acid hydrophobics were high through UV/H2O2, process, while hydrophilics' efficiencies were lower. The experimental results showed that organic molecules with molecular weight over 10,000 contributed greatly to UV254, ADMI7.6 and DOC removal rate.

O3 and UV/O3 oxidation of organic constituents of biotreated municipal wastewater.

Dissolved organic matter (DOM) in the biotreated effluent of a municipal wastewater treatment plant was separated by XAD-8 and XAD-4 resins into four fractions: hydrophobic acids, non-acid hydrophobics, transphilics and hydrophilics. Ozonation with and without ultraviolet (UV) enhancement removed most UV-absorbing substances in the first 30 min achieving 78% and 63% reduction in UV254, respectively; the UV enhancement resulted in a greater reduction in dissolved organic carbon (DOC) (90% vs. 36%). Ozone reacted sequentially with aromatic hydrophobics, transphilics, and then hydrophilics; however, under UV, it reacted with all four organic fractions simultaneously. Low-MW hydrophilics were the most abundant fraction in the ozone-treated effluent.

[Diffusion coefficients of ammonia, nitrate and nitrite in cell-free and cell-containing PVA gel membranes].

The cell-free PVA gel membrane and cell-containing PVA gel membrane were prepared by iterative freezing and thawing, and the diffusion coefficients of ammonia, nitrate and nitrite in PVA gel membranes were determined. The effect of the conditions of preparing PVA gel membranes and cell concentration on the diffusion coefficients of ammonia in PVA gel membranes were investigated. The results shown the diffusion coefficients of ammonia in PVA gel membranes decreased while the iteration times of freezing-thawing or PVA concentration or cell concentration increased. The diffusion coefficients of ammonia, nitrate and nitrite in cell-free PVA gel membranes (PVA concentration was 15%) were 0.69 x 10(-9) m2/s, 0.52 x 10(-9) m2/s, and 0.56 x 10(-9) m2/s, respectively. The diffusion coefficients of ammonia, nitrate and nitrite in cell-containing PVA gel membranes (the cell concentration was 60 g/L) were 0.55 x 10(-9) m2/s, 0.46 x 10(-9) m2/s, and 0.45 x 10(-9) m2/s, respectively.