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Abstract To reveal the influence of the diversity of precursors on the formation of environmental persistent free radicals (EPFRs), pomelo peel (PP) and its physically divided portion, pomelo cuticle (PC), and white fiber (WF) were used as precursors to prepare six hydrochars: PPH-Fe, PCH-Fe, WFH-Fe, PPH, PCH, and WFH with and without Fe(III) addition during hydrothermal carbonization (HTC). PPH-Fe and WFH-Fe had higher EPFRs content (9.11 × 1018 and 8.25 × 1018 spins·g−1) compared to PPH and WFH (3.33 × 1018 and 2.96 × 1018 spins·g−1), indicating that iron-doping favored EPFRs formation. However, PCH-Fe had lower EPFRs content (2.78 × 1018 spins·g−1) than PCH (7.95 × 1018 spins·g−1), possibly due to excessive iron leading to the consumption of the generated EPFRs. For another reason, the required Fe(III) amount for EPFRs formation might vary among different precursors. PC has a lower concentration of phenolic compounds but 68–97% fatty acids, while WF and PP are rich in cellulose and lignin. In the Fenton-like reaction, oxygen-centered radicals of hydrochar played a significant role in activating H2O2 and efficiently degrading bisphenol A (BPA). Mechanisms of reactive oxygen species (ROS) generation in hydrochar/H2O2 system were proposed. EPFRs on hydrochar activate H2O2 via electron transfer, creating ·OH and 1O2, leading to BPA degradation. More importantly, the embedded EPFRs on the hydrochar's inner surface contributed to the prolonged Fenton-like reactivity of PPH-Fe stored for 45 days. This study demonstrates that by optimizing precursor selection and iron doping, hydrochars can be engineered to maximize their EPFRs content and reactivity, providing a cost-effective solution for the degradation of hazardous pollutants. Graphical abstract

To reveal the influence of the diversity of precursors on the formation of environmental persistent free radicals (EPFRs), pomelo peel (PP) and its physically divided portion, pomelo cuticle (PC), and white fiber (WF) were used as precursors to prepare six hydrochars: PPH-Fe, PCH-Fe, WFH-Fe, PPH, PCH, and WFH with and without Fe(III) addition during hydrothermal carbonization (HTC). PPH-Fe and WFH-Fe had higher EPFRs content (9.11 × 1018 and 8.25 × 1018 spins·g−1) compared to PPH and WFH (3.33 × 1018 and 2.96 × 1018 spins·g−1), indicating that iron-doping favored EPFRs formation. However, PCH-Fe had lower EPFRs content (2.78 × 1018 spins·g−1) than PCH (7.95 × 1018 spins·g−1), possibly due to excessive iron leading to the consumption of the generated EPFRs. For another reason, the required Fe(III) amount for EPFRs formation might vary among different precursors. PC has a lower concentration of phenolic compounds but 68–97% fatty acids, while WF and PP are rich in cellulose and lignin. In the Fenton-like reaction, oxygen-centered radicals of hydrochar played a significant role in activating H2O2 and efficiently degrading bisphenol A (BPA). Mechanisms of reactive oxygen species (ROS) generation in hydrochar/H2O2 system were proposed. EPFRs on hydrochar activate H2O2 via electron transfer, creating ·OH and 1O2, leading to BPA degradation. More importantly, the embedded EPFRs on the hydrochar's inner surface contributed to the prolonged Fenton-like reactivity of PPH-Fe stored for 45 days. This study demonstrates that by optimizing precursor selection and iron doping, hydrochars can be engineered to maximize their EPFRs content and reactivity, providing a cost-effective solution for the degradation of hazardous pollutants. Article Highlights: Characteristics and mechanisms for the generation and consumption of EPFRs were proposed. To favor g3-type EPFRs formation, the quantity of Fe(III) and aromatic compounds of the biomass should be matched. The g3-type EPFRs on hydrochars played a major role in the Fenton-like reaction. The external EPFRs of hydrochars were consumed easily while the internal EPFRs persisted during long-term storage. [ABSTRACT FROM AUTHOR]

The fabrication of low-cost, highly efficient, environmentally friendly, and easily separable metal-free heterogeneous catalysts for environmental remediation remains a challenge. In this study, granular nitrogen-doped highly developed porous carbons with a particle size of 0.25–0.30 mm were prepared by preoxidation and subsequent NH3 modification of a commercially available coconut-based activated carbon, and used to activate peroxymonosulphate (KHSO5) or hydrogen peroxide (H2O2) to degrade bisphenol A (BPA). The nitrogen-doped carbon (ACON-950) prepared by NH3 modification at 950 °C, with the addition of only 0.15 g/L could remove 100% of 50 mg/L BPA in 150 min, and more than 90% of the removed BPA was due to degradation. The removal rates of total organic carbon of ACON-950/KHSO5 and ACON-950/H2O2 systems reached 60.4% and 66.2% respectively, indicating the excellent catalytic activity of ACON-950. The reaction rate constant was significantly positively correlated with the absolute content of pyridinic N (N-6) and graphitic N (N-Q) and negatively and weakly positively correlated with pyrrolic N (N-5) and defects. Quenching experiments combined with electron paramagnetic resonance demonstrated that singlet oxygen was the dominant reactive oxidative species for BPA degradation. ACON-950 was characterized before and after the degradation reaction using N2 adsorption–desorption analyzer, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The results confirmed the prominent contribution of both the N-6 and N-Q to the catalytic performance of nitrogen-doped carbons. The reusability of ACON-950 and its application in actual water bodies further demonstrated its remarkable potential for the remediation of organic pollutants in wastewater. [ABSTRACT FROM AUTHOR]

To achieve efficient degradation of organic pollutants, two critical objectives are enhancing photogenerated carrier separation and expanding the spectral response range. In this study, we synthesized atom-sharing Bi/Bi 4 O 5 Br 2 :Yb3+,Tm3+ (Bi/BYT) heterojunctions with surface plasmon resonance (SPR) effects and upconversion (UC) by employing self-sacrificial Bi 4 O 5 Br 2 :Yb3+,Tm3+ (BYT) fractions as a source of metallic Bi. Results revealed that the optimal Bi/BYT-2 catalyst exhibited the highest BPA degradation efficiency within 120 min, representing a significant 1.3-fold improvement over BYT alone. This outstanding catalytic performance can be attributed to the synergistic interplay between UC fluorescence, the unique SPR effect of Bi metal, and the atom-sharing heterojunction. These factors effectively broaden the spectral absorption range and significantly enhance the separation and utilization efficiency of photoinduced carriers. This study lays the groundwork for the development and design of novel atomic-level contact heterojunctions, offering insights into enhancing photocatalytic efficiency through plasmon resonance and UC fluorescence on non-precious metal surfaces. [ABSTRACT FROM AUTHOR]

Mechanism of PMS activation by the MPCBs/PMS system. [Display omitted] Magnetic carbon-based catalysts are promising materials for advanced oxidation processes, offering both high catalytic activity and environmental friendliness, and hold great potential in environmental remediation. In this work, Fe and Co zeolite imidazole frameworks (ZIFs) derived micron-sized magnetic porous carbon beads (MPCBs) were prepared by phase inversion and following the carbonization procedure, and the morphological and structural characteristics of the MPCBs were confirmed. The presence of pores and channels in the MPCBs provides a specific microenvironment for the for the catalysis of the core. Bisphenol A (BPA) was selected for the targeted pollutant, and the catalytic experiments confirmed that the effective catalytic activity of MPCBs in the presence of peroxymonosulfate (PMS), which could almost completely degrade BPA in 20 min with a reaction rate of 0.368 min−1. Furthermore, the MPCBs were used to effectively bacterial inactivation. Intermediate products of the BPA degradation process were validated and the toxicological studies showed a gradual decrease in toxicity, indicating effective reduction of potential hazards. The macroscopic preparation methods we developed for MPCBs that is promising for industrial applications and has the potential to cope with complex environmental remediation. [ABSTRACT FROM AUTHOR]

To study the degradation of bisphenol A (BPA) of the different Bi2WO6-based composite photocatalyst under visible-light irradiation, a novel Z-scheme Cu2S/reduced graphene oxide/Bi2WO6 (Cu2S/RGO/Bi2WO6) was successfully synthesised by solvothermal-hydrothermal method, andBi25FeO40/RGO/Bi2WO6 was introduced for comparative study. The Cu2S/RGO/Bi2WO6 was characterised by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) test and X-ray photoelectron spectrometer (XPS).TheBi2WO6,Cu2S/RGO/Bi2WO6andBi25FeO40/RGO/Bi2WO6 were used to degrade bisphenol (BPA) under visible light, respectively, and in addition peroxymonosulfate (PMS) was used as an additive for the Cu2S/RGO/Bi2WO6 to degrade BPA. For Cu2S/RGO/Bi2WO6@PMS, the removal ratio of BPA is 91.0% in 40 minutes, which is much higher than pure Bi2WO6 (22.0%),Cu2S/RGO/Bi2WO6 without PMS (56.1%) and Bi25FeO40/RGO/Bi2WO6 (48.3%). A Z-scheme photocatalytic mechanism was proposed for Cu2S/RGO/Bi2WO6@PMSbased on the results of UV–vis DRS, PL analysis and Mott–Schottky curve. There are four factors that contribute to CuS2/RGO/Bi2WO6with PMS to achieve excellent photocatalytic performance: 1. The larger specific area; 2. the higher absorption capacity of visible light; 3. RGO can act as a very important role to significantly accelerate electron transfer, and 4. PMS can be activated to generate •SO4− for BPA degradation. [ABSTRACT FROM AUTHOR]

Bisphenol A (BPA), one of the most widely used plasticizers, is an endocrine-disrupting chemical that is released from plastic products. The aim of this study was to screen and characterize bacteria with excellent BPA-degrading abilities for application in foods. BPA degradation ability was confirmed in 127 of 129 bacterial strains that were isolated from fermented soybean foods. Among the strains, B. subtilis P74, which showed the highest BPA degradation performance, degraded 97.2% of 10 mg/L of BPA within 9 h. This strain not only showed a fairly stable degradation performance (min > 88.2%) over a wide range of temperatures (30–45 °C) and pH (5.0–9.0) but also exhibited a degradation of 63% against high concentrations of BPA (80 mg/L). The metabolites generated during the degradation were analyzed using high-performance liquid chromatography–mass spectrometry, and predicted degradation pathways are tentatively proposed. Finally, the application of this strain to soybean fermentation was conducted to confirm its applicability in food. [ABSTRACT FROM AUTHOR]

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Bisphenol A (BPA) is an emerging endocrine disruptor commonly found in industrial wastewater. Horseradish peroxidase (HRP) is a plant enzyme that is effective in removing BPA in the presence of hydrogen peroxide, and immobilization techniques can improve its stability in use as well as its catalytic efficiency. This study constructs the MIL-100(Fe) materials with hierarchical pores and peroxidase-like activity as carriers for immobilizing HRP. The relevant characterization proved that the crystal structure and chemical composition of HP-MIL-100(Fe) (Hierarchically Porous MIL-100(Fe)) were the same as that of standard MIL-100(Fe), and the specific surface area reached 940.88 m2 with an average mesopore size of 5.12 nm. HRP was immobilized by diffusion and covalent binding method and the immobilized amount was obtained as 78.49 mg/g. Compared to HRP, HRP@HP-MIL-100(Fe) has better chemical stability as well as substrate affinity. The results of degradation experiments showed that HRP@HP-MIL-100 (Fe) degraded BPA 71% more than free HRP at the fifth minute, reaching 90.83%. This research demonstrates the potential of immobilized enzyme technology for future application in the sustainable degradation of phenolic effluents, contributing to cleaner production in industry as well as environmental protection. • A substitution and hydrolysis-based strategy to construct hierarchical porous MOFs for enzyme immobilization, with the average pore size of mesopores enlarged to 5.12 nm. • The immobilized HRP loading can reach up to 78.49 mg/g, which leads to an improvement in relative enzyme activity, particularly with a 22.80% enhancement observed under acidic conditions. • The stability and reusability of the enzyme immobilized in HP-MIL-100(Fe) were greatly improved. • HRP@HP-MIL-100(Fe) exhibits rapid and efficient degradation characteristics towards BPA, achieving a degradation rate of 90.83% within 5 min. [ABSTRACT FROM AUTHOR]

• TiOCs effectively adjusted the electronic structure of CN. • TiOCs-CN acted as both PMS activator and photocatalyst. • BPA can be effectively degraded under various environments. • BPA removal is dominated via both radical and non-radical pathway. Photocatalytic peroxymonosulfate (PMS) activation process is promising for the organic wastewater treatment. A simple amide bonding strategy has been developed to synthesized Ti-oxo clusters (TiOCs)-g-C 3 N 4 (TiOCs-CN) catalyst. The prepared TiOCs-CN was used to remove bisphenol A (BPA) under simulated sunlight-driven PMS. The experimental and computational results demonstrate that the incorporation of TiOCs can efficiently regulate the electronic structure of CN. Thus, an excellent performance with a BPA removal rate of 100 % and a total organic carbon (TOC) removal rate of 87.2 % within 40 min was achieved in the AM 1.5/PMS-TiOCs-CN system. Among, the reaction rate constant of AM 1.5/PMS-TiOCs-CN (97.24 × 10−3 min−1) is higher than that of AM 1.5/PMS-CN (25.10 × 10−3 min−1) by nearly 4 times. The synergistic effect of photocatalytic PMS activation greatly facilitated the generation of reactive radicals and obviously increased the removal rate of BPA. This work can offer inspiration for rational design of high efficiency photocatalysts in the PMS oxidation process for organic wastewater remediation. [ABSTRACT FROM AUTHOR]

[Display omitted] • UHP has higher electron utilization and targeting efficiency compared to H 2 O 2. • The nonpolar performance of O-O in UHP in water is weaker than H 2 O 2. • UHP undergoes electron transfer easily with Fe2+ to form more stable complexes. • Less energy is required for the degradation of BPA by UHP/Fe(II) An advanced Fenton technique using urea peroxide (UHP) as an oxidant was studied for the degradation of bisphenol A (BPA) in aqueous solution. Compared to the H 2 O 2 /Fe(II) system, the UHP/Fe(II) system performs noticeably better in terms of degradation and requires less catalyst. The mechanism by which UHP exhibits unique and remarkable properties has been elucidated at the molecular level (bond order, AIM analysis, ELF, Spin Population number, electron difference density maps) by density functional theory (DFT) calculations. The ELF and the electron density difference revealed that UHP created an intermediate coordination compound with six-coordinated iron (II), facilitating electron transfer and the disruption of O-O bonds because of the feeble O-O strength, leading to an increase in hydroxyl radicals. Consequently, UHP increases the rate of electron usage and targeting efficiency, which accelerates the breakdown of BPA. targeting efficiency, which accelerates the breakdown of BPA. Based on the intermediates determined by LC-MS/MS, the possible degradation pathway of BPA in the UHP/Fe(II) system were proposed, which was verified to be a lower energy consumption pathway by calculating the reaction energy barriers. It is expected to be an advanced Fenton technology with practical engineering applications potential, due to the advantages of wider pH window, lower energy consumption and higher electron utilization. [ABSTRACT FROM AUTHOR]

This work aimed to demonstrate Cu2O/Al2O3 as a catalyst of the photo-Fenton process in the UV and visible spectra. Cu2O nanoparticles were synthesized by laser ablation in liquid and supported on Al2O3. The catalytic activity of the resulting solid was assessed in the mineralization of bisphenol A (BPA). The studied variables were type of Al2O3 α   and   γ , Cu content (0.5 and 1%), and H2O2 concentration (1, 5, and 10 times the stoichiometric amount). The response variables were BPA concentration and total organic carbon (TOC) removal percentage. The presence of Cu2O nanoparticles (11 nm) with an irregular sphere-like shape was confirmed by transmission electron microscopy (TEM) and their dispersion over the catalytic surface was verified by energy-dispersed spectroscopy (EDS). These particles improve ·OH radical production, and thus a 100% removal of BPA is achieved along with ca. 91% mineralization in 60 min. The BPA oxidation rate is increased one order of magnitude compared to photolysis and doubles that for H2O2 + UV. An increase of 40% in the initial oxidation rate of BPA was observed when switching from α-Al2O3 to γ-Al2O3. 4-hydroxybenzaldehyde, 4-hydroxybenzoic acid, acetaldehyde, and acetic acid are the BPA oxidation by-products identified using LC/MS and based on this a reaction pathway was proposed. Finally, it was also concluded that the synthesized catalyst exhibits catalytic activity not only in the UV spectrum but also in the visible one under circumneutral pH. Therefore, Cu2O/Al2O3 can be recommended to conduct a solar photo-Fenton reaction that can degrade other types of molecules. [ABSTRACT FROM AUTHOR]

Bisphenol A (BPA), one of the most widely used plasticizers, is an endocrine-disrupting chemical that is released from plastic products. The aim of this study was to screen and characterize bacteria with excellent BPA-degrading abilities for application in foods. BPA degradation ability was confirmed in 127 of 129 bacterial strains that were isolated from fermented soybean foods. Among the strains, B. subtilis P74, which showed the highest BPA degradation performance, degraded 97.2% of 10 mg/L of BPA within 9 h. This strain not only showed a fairly stable degradation performance (min > 88.2%) over a wide range of temperatures (30–45 °C) and pH (5.0–9.0) but also exhibited a degradation of 63% against high concentrations of BPA (80 mg/L). The metabolites generated during the degradation were analyzed using high-performance liquid chromatography–mass spectrometry, and predicted degradation pathways are tentatively proposed. Finally, the application of this strain to soybean fermentation was conducted to confirm its applicability in food.

Designing and constructing novel discrete architecture for quantum dots modified ultrathin hollow nanotube Bi 2 Sn 2 O 7 /Bi 4 O 5 I 2 S-scheme heterojunctions for the first time in this work is an ideal strategy to improve the photocatalytic activity. As expected, the Bi 2 Sn 2 O 7 /Bi 4 O 5 I 2 heterojunction exhibited outstanding performance of degradation bisphenol A (BPA), the rate constant of Bi 2 Sn 2 O 7 /Bi 4 O 5 I 2 heterojunction was 1.7 and 41.8 times higher than that of Bi 4 O 5 I 2 and Bi 2 Sn 2 O 7 , respectively. The promoted activity could be attributed to the spatial separation of photogenerated carriers as well as redox reaction sites due to the discrete structure, and the enhanced charge separation due to the S-scheme mechanism via Bi-O channels as derived from DFT calculations. Furthermore, Bi 2 Sn 2 O 7 /Bi 4 O 5 I 2 heterojunction exhibited unprecedented ultra-efficient in BPA degradation compared to other published Bi-based catalysts, and excellent performance under actual sunlight contributes to its prospective practical application. This strategy affords a novel approach for fabricating discrete S-scheme heterojunctions photocatalysts with high-efficiency, strong-stable, and sustainable. [Display omitted] • Novel quantum dots modified Bi 2 Sn 2 O 7 /Bi 4 O 5 I 2 S-scheme heterojunction was fabricated. • The discrete structure realizes separation of photogenerated e- and h+ and redox reaction sites. • The formed Bi-O bonds strengthen the interfacial coupling and work as fast electron transfer paths. • Bi 2 Sn 2 O 7 /Bi 4 O 5 I 2 heterojunction exhibited unprecedented ultra-efficient in BPA degradation. [ABSTRACT FROM AUTHOR]

[Display omitted] • BPA was efficiently degraded by radical addition, C–C cleavage and hydroxylation. • Toxicity assessment revealed the risk reduction of BPA during EOP degradation. • C atoms on ortho and para sites of BPA/phenol were more preferable be attacked. • Reaction time and rate of BPA/phenol with radical were affected by their structure. • Similar compounds' structure affected the dominant radical and degradation process. Parent structures can greatly affect the free radicals attack, and the corresponding degradation efficiency and toxicity of organics, while the further influence mechanism of compounds' structure with similar parent structure still needs to be revealed. Herein, the electrochemical oxidation process (EOP) was applied to explore the effects of similar pollutants' (bisphenol-A(BPA)/phenol) structure on dominant radical and degradation mechanism, and comprehensively assessed the ecotoxicity of the BPA degradation intermediates/products. The removal efficiency of BPA achieved 84.2 %–98.3 % in all the experimental conditions. BPA degradation pathways, mainly including radical adduct formation, C–C bond cleavage and hydroxylation, were proposed based on density functional theory (DFT) calculation and intermediates detection. Toxicity assessment revealed the reducing trend of risk during BPA degradation, and the acute/chronic toxicity (toxic/very-toxic) of BPA were reduced to not-harmful/harmful. The slight increased toxicity in initial stage was due to the generated chlorinated products from the highest contribution of radical chlorine species (RCS). The comparison of BPA/phenol degradation demonstrated the influence of molecular structure on degradation even with similar parent structure. It seemed that the reaction time and rate constants between BPA/phenol and radicals were affected (achieved 5 orders of magnitude), which can further influence radical contributions (BPA: RCS (63.8 %) >OH (30.6 %) > direct oxidation (5.5 %), phenol: OH (78.78 %) > RCS (10.7 %) > direct oxidation (10.6 %)) and preferable attacking sites, and thus degradation mechanism and efficiencies. These results provided new insights into novel anodes/catalysts design during advanced oxidation process to improve their degradation performance and practical application safety. [ABSTRACT FROM AUTHOR]

This study reported a photoelectric co-catalyst system of jet-flow reactor for efficient mineralization of Bisphenol A (BPA), where H 2 O 2 was photoelectro-generated in situ from O 2 reduction on gas diffusion electrodes fabricated by nitrogen-doped porous carbon and graphitic carbon nitride (NPC/g-C 3 N 4). Current density, aeration rate, amount of MoS 2 and FeSO 4 catalyst in the jet-flow reactor photoelectrocatalysis system for BPA removal were investigated. The NPC/g-C 3 N 4 cathodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), and the electrochemical workstation. The results show that at pH 7, the NPC/g–C 3 N 4 –(60%) has the highest rate of electrical generation hydrogen peroxide. When the pH rised, at pH values of 7, the cumulative of hydrogen peroxide increased, when the solution get slight alkaline, it was gradually decreased. Compared with the traditional electro-Fenton technology, the photoelectric method of co-catalysis has strong ·OH production rate and high oxidation ability. A possible mechanism for BPA degradation was oxidized by hydroxyl radical (·OH), resulting in the formation of shorter chain bisphenol A (BPA), which followed the same reaction cycle as BPA until it was mineralized. The removal rate of BPA can reach 100% within 20 min, the TOC removal rate up to 90%. This work provides new opinion into the development of a photoelectric collaborative system for H 2 O 2 generation and the fast BPA degradation. • NPC/g-N 3 C 4 electrode exhibit good photoelectrochemical properties under UV light irradiation. • During the degradation of bisphenol A, both electrocatalysis and photocatalysis produce a synergistic effect. • The functionalize mesoporous carbon electrode can effectively generate H 2 O 2 via photoelectrochemical reduction of O 2. [ABSTRACT FROM AUTHOR]

Piezo-electricity, as a unique physical phenomenon, demonstrates high effectiveness in capturing the environmental mechanical energy into polarization charges, offering the possibility to activate the advanced oxidation processes via the electron pathway. However, information regarding the intensification of Fe(VI) through piezo-catalysis is limited. Therefore, our study is the first to apply Bi 2 WO 6 nanoplates for piezo-catalyzation of Fe(VI) to enhance bisphenol A (BPA) degradation. Compared to Fe(VI) alone, the Fe(VI)/piezo/Bi 2 WO 6 system exhibited excellent BPA removal ability, with the degradation rate increased by 32.6% at pH 9.0. Based on the experimental and theoretical results, Fe(VI), Fe(V), Fe(IV) and •OH were confirmed as reaction active species in the reaction, and the increased BPA removal mainly resulted from the enhanced formation of Fe(IV)/Fe(V) species. Additionally, effects of coexisting anions (e.g., Cl−, NO 3 −, SO 4 2− and HCO 3 −), humic acid and different water matrixes (e.g., deionized water, tap water and lake water) on BPA degradation were studied. Results showed the Fe(VI)/piezo/Bi 2 WO 6 system still maintained satisfactory BPA degradation efficiencies under these conditions, guaranteeing future practical applications in surface water treatment. Furthermore, the results of intermediates identification, ECOSAR calculation and cytotoxicity demonstrated that BPA degradation by Fe(VI)/piezo/Bi 2 WO 6 posed a diminishing ecological risk. Overall, these findings provide a novel mechanical energy-driven piezo-catalytic approach for Fe(VI) activation, enabling highly efficient pollutant removal under alkaline condition. [Display omitted] • Bi 2 WO 6 nanoplates was first used for piezo-catalyzation of Fe(VI). • The Fe(VI)/piezo/Bi 2 WO 6 system significantly enhanced the removal of BPA. • Piezo-activation enhanced the weak reactivity of Fe(VI) under alkaline conditions. • Bi 2 WO 6 mediated piezo-catalysis effectively fastened the formation of Fe(IV)/Fe(V). • Piezo-activation of Fe(VI) provides an energy-saving method for water remediation. [ABSTRACT FROM AUTHOR]

Piezo-electricity, as a unique physical phenomenon, demonstrates high effectiveness in capturing the environmental mechanical energy into polarization charges, offering the possibility to activate the advanced oxidation processes via the electron pathway. However, information regarding the intensification of Fe(VI) through piezo-catalysis is limited. Therefore, our study is the first to apply Bi 2 WO 6 nanoplates for piezo-catalyzation of Fe(VI) to enhance bisphenol A (BPA) degradation. Compared to Fe(VI) alone, the Fe(VI)/piezo/Bi 2 WO 6 system exhibited excellent BPA removal ability, with the degradation rate increased by 32.6% at pH 9.0. Based on the experimental and theoretical results, Fe(VI), Fe(V), Fe(IV) and •OH were confirmed as reaction active species in the reaction, and the increased BPA removal mainly resulted from the enhanced formation of Fe(IV)/Fe(V) species. Additionally, effects of coexisting anions (e.g., Cl - , NO 3 - , SO 4 ), humic acid and different water matrixes (e.g., deionized water, tap water and lake water) on BPA degradation were studied. Results showed the Fe(VI)/piezo/Bi 2- and HCO 3 system still maintained satisfactory BPA degradation efficiencies under these conditions, guaranteeing future practical applications in surface water treatment. Furthermore, the results of intermediates identification, ECOSAR calculation and cytotoxicity demonstrated that BPA degradation by Fe(VI)/piezo/Bi - ), humic acid and different water matrixes (e.g., deionized water, tap water and lake water) on BPA degradation were studied. Results showed the Fe(VI)/piezo/Bi 2 WO 6 system still maintained satisfactory BPA degradation efficiencies under these conditions, guaranteeing future practical applications in surface water treatment. Furthermore, the results of intermediates identification, ECOSAR calculation and cytotoxicity demonstrated that BPA degradation by Fe(VI)/piezo/Bi 2 WO 6 posed a diminishing ecological risk. Overall, these findings provide a novel mechanical energy-driven piezo-catalytic approach for Fe(VI) activation, enabling highly efficient pollutant removal under alkaline condition., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This study demonstrated, for the first time, Fe(III)/peroximonosulphate (PMS) could be an efficient advanced oxidation process (AOP) for wastewater treatment. Bisphenol A (BPA) was chosen as a model pollutant in the present study. Fe(III)-activated PMS system proved very effective to eliminate 92.18% of BPA (20 mg/L) for 30-min reaction time at 0.50 mM PMS, 1.5 g/L Fe(III), pH 7.0. The maximum degradation of BPA occurred at neutral pH, while it was suppressed at both strongly acidic and alkaline conditions. Organic and inorganic ions can interfere with system efficiency either positively or negatively, so their interaction was thoroughly investigated. Furthermore, the presence of organic acids also affected BPA degradation rate, especially the addition of 10 mM citric acid decreased the degradation rate from 92.18 to 66.08%. Radical scavenging experiments showed that SO4•– was the dominant reactive species in Fe(III)/PMS system. A total of 5 BPA intermediates were found by using LC/MS. A possible degradation pathway was proposed which underwent through bridge cleavage and hydroxylation processes. Acute toxicity of the BPA degradation products was assessed using Escherichia coli growth inhibition test. These findings proved to be promising and economical to deal with wastewater using iron mineral for the elimination of organic pollutants. [ABSTRACT FROM AUTHOR]

[Display omitted] • Breaking symmetry of carbon nitride skeleton with establishing in-plane electric field for superior charge migration efficiency. • Inducing n → π* electron transition by embedding pyridine ring to promote optical absorption. • pyCN achieved high hydrogen evolution rate with simultaneously oxidation of bisphenol A under visible light. Breaking symmetry of polymeric carbon nitride (CN) skeleton by heteroatomic substitution can induce in-plane polar electric field, thus promoting the migration and separation of photoexcited charge carriers. Herein, a carbon-doped CN (pyCN) by embedding pyridine ring was prepared through a skeleton modification strategy. Owing to the n → π* electron transition and the formed in-plane polar electric field, the obtained pyCN displayed obvious extended optical absorption and photoinduced charge migration efficiency in comparison with pure CN. The optimized photocatalytic H 2 evolution rate over pyCN reached 242.9 μmol·h−1, which is 6 times of that over pure CN with TEOA as a sacrifice. Additionally, the wavelength for H 2 evolution over pyCN extends to 550 nm while that is 450 nm over pure CN, demonstrating an improved efficiency of sunlight utilization after skeleton modification. In addition, pyCN showed synergistic oxidation of bisphenol A (BPA) during hydrogen generation under visible light. The conversion efficiency of BPA reached 18.7 % in 24 h according to the external standard analysis. This work provides an efficient approach for enhancing optical absorption and inhibiting photoexcited charge recombination for higher photocatalytic performance and wilder applications. [ABSTRACT FROM AUTHOR]

Abstract In this study, we have synthesized hierarchical TiO 2 @In 2 O 3 heteroarchitecture photoanodes via a hydrothermal method and studied their interfacial charge carrier dynamics through water splitting and organic decomposition. Photoelectrochemical measurements show that the IN-0.4 exhibits an obvious enhancement in photocurrent density compared to the pristine TiO 2. Electrochemical impendence spectroscopy (EIS) and Time-resolved photoluminescence (PL) have been employed to study the charge recombination in TiO 2 @In 2 O 3 nanostructure. The surface passivation of TiO 2 nanorods (NRs) with In 2 O 3 nanostructures helps to the suppression of the surface defects. The surface-passivated photoanode (IN-0.4) has demonstrated the improved hydrogen generation activity (125 μmol∙h−1) of TiO 2 nanorods (NRs) with In 2 O 3 nanostructures during water splitting and organic decomposition. The probable causes of the enhancement in hydrogen evolution could be due to (i) enhanced photogenerated electron transport (ii) increased active surface area with In 2 O 3 and/or (iii) catalytic activity of In 2 O 3. Moreover, the photoelectrocatalytic activities of IN-0.4 were slight affect during degradation of Bisphenol A and methyl orange dye, which might be due to the lower hole mobility in TiO 2 @In 2 O 3 heteroarchitecture photoelectrodes. These sightings and proposed schematic model can help to understand the charge transfer dynamics in hierarchical TiO 2 @In 2 O 3 heteroarchitecture photoelectrodes as well as designing multifaceted photoelectrodes for solar energy conversion. Graphical abstract A detailed mechanism of the interfacial charge carrier dynamics in hierarchical TiO 2 @In 2 O 3 photoelectrodes during photoelectrochemical hydrogen generation and BPA degradation performances is described. Unlabelled Image Highlights • TiO 2 @In 2 O 3 heteroarchitecture photoanode was prepared by facile hydrothermal method. • TiO 2 @In 2 O 3 heteroarchitecture photoanode shows excellent solar hydrogen generation. • 125 μmol∙h−1 hydrogen generation and 94% MO degradation was achieved. • In-depth interfacial electron transfer mechanism was proposed. • This work contributes a deep insight to the interfacial charge carrier dynamics during photoelectrochemical process. [ABSTRACT FROM AUTHOR]

Highlights • A novel and high-efficient Fe 3 O 4 -α-MnO 2 nanoflower-like catalyst was synthesized to activate PS for BPA degradation. • The synergistic effect promoted the circulation of Fe3+/Fe2+ and Mn4+/Mn3+. • The presence of hydroxyl groups on the catalyst surface also played a key role in PS activation. • The possible degradation pathway of BPA was proposed in Fe 3 O 4 -α-MnO 2 /PS system. Abstract A novel and high-efficiency Fe 3 O 4 -α-MnO 2 nanoflower-like catalyst was synthesized using a two-step hydrothermal method. The catalyst was used to activate persulfate (PS) to degrade bisphenol A (BPA) in aqueous phase. The mechanism of the Fe 3 O 4 -α-MnO 2 /PS system was investigated. X-ray photoelectron spectra and cyclic voltammograms showed that the mixed valence of Fe 3 O 4 -α-MnO 2 was favorable to electron transfer between Fe and Mn elements. Apparently, this process promoted the circulation of Fe2+/Fe3+ and Mn3+/Mn4+, increasing the effectiveness of the catalyst to activate the PS. In addition, with ATR-FTIR analysis, the influence of phosphate confirmed the presence of OH groups on the Fe 3 O 4 -α-MnO 2 surface. Thus, these groups played crucial roles in the PS activation. Sulfate radicals were reacting species of great importance in BPA degradation. The degradation intermediates were also detected via GC–MS analysis, and the possible BPA degradation pathway was proposed. [ABSTRACT FROM AUTHOR]

Carbon vacancies and Rh 2 O 3 nanoparticles were sequentially introduced into CN to accelerate photo-generated electron and hole transfer simultaneously, and the effect of defect and cocatalyst on the photodegradation process was systematically analyzed, resulting in high performance of degradation 10 ppm BPA within 15 min under visible light condition. [Display omitted] • Ultrafine Rh 2 O 3 nanoparticles (∼5 nm) are dispersed on the surface of CN. • The C vacancies and Rh 2 O 3 can respectively promote the transfer of electrons and holes to inhibit the recombination of excitons. • V C -CN 7.5 -Rh 2 O 3 -900 can degrade 10 ppm BPA in 15 min showing excellent degradation rate. The sluggish charge transfer and fast recombination of charge carriers is a determining factor limiting photocatalytic efficiency of carbon nitride. Herein, carbon vacancies and Rh 2 O 3 nanoparticles were sequentially introduced into CN to accelerate photo-generated electron and hole transfer simultaneously, thereby improving the photocatalytic performance of CN to achieve the complete removal of Bisphenol A (BPA) in 15 min. Mechanism analyses reveal that the modification of the carbon vacancies regulates the active charge carriers, excitons and trap states, thus enhances the carrier separation capabilities and light absorption. Meanwhile, the in situ photodeposited Rh 2 O 3 nanoparticles, as a hole-transfer mediator, maximally suppress recombination of photogenerated charges. These synergistic effects result in promoting the separation and transfer of charge carriers and thus improving photocatalytic performances. This strategy can serve as guideline for the reasonable design of efficient photocatalysts for phenolic wastewater remediation. [ABSTRACT FROM AUTHOR]

Bi-based semiconductor photocatalyst represented by Bi 2 MoO 6 (BMO) has obvious advantages in the degradation of bisphenol A (BPA), but three prominent problems that restrict the improvement of photocatalytic performance, namely, insufficient solar absorption, less active sites and serious photogenerated carrier recombination, need to be solved urgently. For this reason, we specially designed a simple structure of B-doped carbon quantum dots (BCQDs) modified BMO nanoflower-like microsphere composite to improve the photocatalytic performance of the system from the above three dimensions. The optimized BCQDs/BMO sample completely degraded BPA within 120 min under simulated sunlight, corresponding to an apparent constant of 0.03453 min−1, while the control sample of CQDs/BMO without B doping only degraded about 84 % of BPA within 160 min, with an apparent coefficient of 0.01138 min−1. Even after filtering out UV components below 400 nm, the degradation performance of the optimal composite catalyst did not decrease. The improved catalytic performance comes from the excellent up-conversion luminescence performance and good electron storage capacity of CQDs on the one hand, and the introduction of B on the other hand can adjust the surface structure of CQDs to generate more active sites and functional interfaces to further promote the catalytic reaction. Free radical trapping and electron spin resonance (ESR) tests have shown that·OH and·O 2 - are the main active substances in the degradation of BPA. The current BCQDs/BMO catalysts, despite their simple structure, can simultaneously improve the catalytic performance from the three important aspects mentioned above, which will guide the design of others semiconductor based photocatalysts. [Display omitted] • Bi 2 MoO 6 nanoflower-like microspheres decorated with B-doped carbon quantum dots (BCQDs) was successfully prepared. • The optimized BCQDs/BMO catalysts were able to completely degrade BPA under both simulated and visible light. • Photocatalytic enhancement comes from unique structural design, interface and energy level modification caused by B doping. • ·O 2 - and ·OH are the main active substances in the degradation of BPA by BCQDs/BMO. [ABSTRACT FROM AUTHOR]

The information on the collaborative removal of nitrate and trace organic contaminants in the thin-layer capping system covered with Fe-loaded biochar (FeBC) is limited. The community changes of bacteria, archaea and fungi, and their co-occurrence patterns during the remediation processes are also unknown. In this study, the optimized biochar (BC) and FeBC were selected as the capping materials in a batch experiment for the remediation of overlying water and sediment polluted with nitrate and bisphenol A (BPA). The community structure and metabolic activities of bacteria, archaea and fungi were investigated. During the incubation (28 d), the nitrate in overlying water decreased from 29.6 to 11.0 mg L−1 in the FeBC group, 2.9 and 1.8 times higher than the removal efficiencies in Control and BC group. The nitrate in the sediment declined from 5.03 to 0.75 mg kg−1 in the FeBC group, 1.3 and 1.1 times higher than those in Control and BC group. The BPA content in the overlying water in BC group and FeBC group maintained below 0.4 mg L−1 during incubation, signally lower than in the Control group. After capping with FeBC, a series of species in bacteria, archaea and fungi could collaboratively contribute to the removal of nitrate and BPA. In the FeBC group, more metabolism pathways related to nitrogen metabolism (KO00910) and Bisphenol degradation (KO00363) were generated. The co-occurrence network analysis manifested a more intense interaction within bacteria communities than archaea and fungi. Proteobacteria, Firmicutes, Actinobacteria in bacteria, and Crenarchaeota in archaea are verified keystone species in co-occurrence network construction. The information demonstrated the improved pollutant attenuation by optimizing biochar properties, improving microbial diversity and upgrading microbial metabolic activities. Our results are of significance in providing theoretical guidance on the remediation of sediments polluted with nitrate and trace organic contaminants. [Display omitted] • Fe-loaded biochar capping is feasible for sediment nitrogen and BPA removal. • Bacteria and archaea communities play key roles in the system. • Specialized but interdependent clusters facilitated remediation process. • Remediation efficiency relates to biochar properties and interdomain interactions. [ABSTRACT FROM AUTHOR]

• Detailed reaction mechanism and kinetics for BPA removal by PAA/Cl– were studied. • Free chlorine and carbon-centered radicals (R-O•) are predominant reactive species. • Activation of PAA by Cl− is ∼107 times higher than its self-decomposition. • R-O• reduces production of disinfection products during treatment of saline water. Peracetic acid is an emerging oxidant and disinfectant for wastewater purification. In this study, we first developed a comprehensive and accurate model to elucidate the reaction mechanisms and simulate reaction kinetics of peracetic acid (PAA, CH 3 C(=O)OOH) activated by chloride (Cl–) based on experimental results and literature. A diversity of experiments methods (e.g., quenching experiments, probe compounds degradation, electron paramagnetic resonance (EPR) measurements) and kinetic modeling were used to determine the reactive species. As a result, carbon-centered radicals and free chlorine reactive species (Cl 2 and HClO) were devoted to BPA degradation in the PAA/Cl− system. The carbon-centered radicals CH 3 C(=O)OO•, CH 3 C(=O)O•, CH 3 OO•, and •CH 3 greatly accelerated BPA degradation with their corresponding kinetics of k CH 3 C(=O)OO•, BPA = 2 × 108 M−1 s−1, k CH 3C(= O)O• , BPA = 2 × 107 M−1 s−1, k •CH 3 , BPA = 2 × 106 M−1 s−1 and k CH 3 OO•, BPA = 2 × 104 M−1 s−1. Dissolved Cl 2 (l) species was also important for BPA degradation with k Cl 2 , BPA of 2 × 107 M−1 s−1, much higher than HClO/ClO− of k HClO, BPA = 1.2 × 101 M−1 s−1 and k ClO − , BPA = 9 × 10−3 M−1 s−1. While free chlorine tends to transform BPA to estrogenic chlorinated organic products, the primary degradation of BPA by carbon-centered radicals results in chlorine-free products, reducing the production of disinfection byproducts during the treatment of saline wastewater. This study improves the knowledge of reaction kinetics and mechanism and reactive species generation in the PAA/Cl– system. [Display omitted] [ABSTRACT FROM AUTHOR]

A novel quinone-modified metal-organic frameworks NH 2 -MIL-101(Fe) was synthesized using a simple chemical method under mild condition. The introduced 2-anthraquinone sulfonate (AQS) can be covalently modified with NH 2 -MIL-101(Fe) and acts as a redox mediator to enhance the degradation of bisphenol A (BPA) via persulfate activation. The obtained AQS-NH-MIL-101(Fe) was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectra, cyclic voltammetry and electrochemical impedance spectroscopy. AQS-NH-MIL-101(Fe) exhibited better catalytic performance compared with NH 2 -MIL-101(Fe) and NH 2 -MIL-101(Fe) with free AQS (NH 2 -MIL-101(Fe)/AQS). That is, AQS-NH-MIL-101(Fe) was proved to be the most effective in that more than 97.7% of BPA was removed. The degradation rate constants (k) of AQS-NH-MIL-101(Fe) was 9-fold higher than that of NH 2 -MIL-101(Fe) and 7-fold higher than NH 2 -MIL-101(Fe)/AQS, indicating that AQS is a great electron-transfer mediator when modified with NH 2 -MIL-101(Fe). Based on the above results, the possible mechanism of catalytic reaction has been investigated in view of the trapping experiments. In addition, the AQS-NH-MIL-101(Fe) catalyst exhibited excellent stability and can be used several times without significant deterioration in performance. [ABSTRACT FROM AUTHOR]

Fe-based carbonaceous materials are a promising catalyst for the degradation of organic pollutants in wastewater through the advanced oxidation. The electron density of Fe centers plays significant role on their degradation performance. However, how to tune the electronic structure of Fe centers to boost catalytic activity is a huge challenge. Herein, FePc/DG hybrid (FePc: iron phthalocyanine; DG: defective graphene) was designed to degrade bisphenol A (BPA). In FePc/DG hybrid, defects with localized regions can transfer electrons to Fe sites, forming electron-rich Fe sites, which is beneficial to boost BPA degradation. As expected, FePc/DG hybrid can efficiently activate the peroxymonosulfate (PMS) and completely remove BPA within 10 min. Meanwhile, FePc/DG hybrid can effectively degrade BPA with an excellent resistance to background interference (pH, ions, and water matrixes) as well as prominent cycle stability (completely remove BPA after five cycles). Density functional theory results demonstrate that FePc/DG hybrid has high adsorption energy for PMS and maximum electron transfer to PMS, which promotes O-O bond cleavage of PMS and boosts BPA degradation. This study further explores the potential of Fe-based materials in degrading pollutants and demonstrates the effect of the electrons around active site on PMS activation. • FePc/DG-PMS system can degrade 100% of BPA in 10 min with eminent cycle stability. • FePc/DG hybrid displays an excellent resistance to pH, ions, and water matrixes. • Electron-rich Fe sites regulated by electron transfer of DG boost BPA degradation. • The FePc/DG has high adsorption energy for PMS and large electron transfer to PMS. [ABSTRACT FROM AUTHOR]

The spatial stereostructure PDI/mpg-C 3 N 4 semiconductor all-organic composites were successfully fabricated via in-situ electrostatic assembling. The spatial stereostructure PDI/mpg-C 3 N 4 composites exhibit outstanding light absorption properties rapid separation and migration abilities of photocarriers, which greatly enhance solar energy utilization. The experiment results exhibit that the BPA degradation rate of the 20% PDI/mpg- C 3 N 4 composite was attained to 3.4 and 7.3 times that of the self-assemble PDI and mpg-C 3 N 4. This provides ideas for constructing organic catalysts with high photocatalytic performance. Fig. 1. a) Schematic diagram of PDI/mpg-C 3 N 4 synthesized by electrostatic attraction; b) PDI/mpg-C 3 N 4 composite material; c) Photocatalytic degradation of BPA by the PDI/mpg-C 3 N 4 composite. [Display omitted] • PDI/mpg-C3N4 all-organic composites with spatial stereostructure are constructed. • The tight π-π interaction favors carrier migration and electron-hole pair separation. • A built-in electric field is formed between PDI and mpg-C 3 N 4. The development of semiconductor photocatalytic technology is still limited to low carrier separation efficiency and secondary contamination of metal ions. The construction of bandgap-matched all-organic semiconductor materials is environmentally friendly and can achieve directional carrier migration and efficient separation. Herein, a series of perylene diimide/mesoporous graphitic carbon nitride (PDI/mpg-C 3 N 4) all-organic composites with spatial stereostructure were successfully fabricated via in-situ electrostatic assembly. The spatial structure composed of perylene diimide/mesoporous graphitic carbon nitride exhibit outstanding light absorption properties and rapid separation and migration abilities of photocarriers, which greatly enhance solar energy utilization. The experiment results exhibit that the bisphenol A (BPA) degradation rate of the 20% perylene diimide/mesoporous graphitic carbon nitride (20% PDI/mpg-C 3 N 4) composite attained to 3.4 and 7.3 times than that of the self-assembled perylene diimide (self-assembled PDI) and mesoporous graphitic carbon nitride (mpg-C 3 N 4). This work provides ideas for constructing organic catalysts with high photocatalytic performance. [ABSTRACT FROM AUTHOR]

A novel porous Z-scheme Ag/AgFeO 2 /g-C 3 N 4 (AAF/UPCN) photocatalyst was successfully prepared via a facile hydrothermal, precipitation and photo-deposition–method. Under visible light irradiation, AAF/UPCN exhibited excellent bisphenol A degradation effect and Staphylococcus aureus inactivation effect compared with porous g-C 3 N 4 (UPCN) and AgFeO 2. The •O 2 ‾ was the major active species during the photocatalytic degradation process. For the photocatalytic mechanism, the photoexcited electrons of UPCN transferred to AgFeO 2 mediated by Ag nanoparticles. This charge migration and separation route was verified collectively by the PL spectra, photoelectrochemical characterizations, chemical scavenger experiments and ESR measurements. Furthermore, the band distribution of catalysts was obtained by DFT calculation. This Ag nanoparticles mediated electron transfer pathway could promote the effective segregation of photoexcited carriers. The synergistic effect of UPCN, AgFeO 2 and Ag in heterostructure could promote the efficient separation of photogenerated charge carriers. This study provides a new strategy for rational design of high-efficient g-C 3 N 4 -based photocatalysts for environmental remediation. [Display omitted] • A novel porous Z-scheme Ag/AgFeO 2 /g-C 3 N 4 photocatalyst was successfully prepared. • The composites exhibited excellent photocatalytic efficiency for BPA and S. aureus. • The carrier transfer mechanism of Ag/AgFeO 2 /g-C 3 N 4 was proposed based on DFT calculation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Bi 2 WO 6 with surface tungsten and oxygen vacancies were synthesized. • Vacancies decrease transfer resistance and increase separation efficiency of charges. • Defective Bi 2 WO 6 shows excellent photocatalytic performance for BPA degradation. • Defective Bi 2 WO 6 exhibits high photocatalytic activity for E. coli inactivation. Organic pollutants and drug-resistant bacteria in water have severely threatened the health of humans and animals, and traditional sewage treatment techniques are restricted by their high cost and complex process. Photocatalysis is one of the most promising tactics to tackle above problems owing to its safety, cleaning and low cost. However, the fast recombination of photogenerated electrons and holes of semiconductors impedes their wide application. In this study, Bi 2 WO 6 with surface tungsten vacancies (WVs) and oxygen vacancies (OVs) were prepared by a facile alkali etching method, and the concentration of vacancies was adjusted by controlling the etching time. The simultaneous introduction of WVs and OVs into Bi 2 WO 6 can not only enhance the separation of photogenerated carriers, but also decrease charge transfer resistance, significantly boosting photocatalytic pollutant degradation and antibacterial performance. As a result, the bisphenol A (BPA) degradation efficiency of Bi 2 WO 6 etched for 2 h (BWO-E2) can reach 90% within 120 min under simulated sunlight irradiation and the Escherichia coli (E. coli) inactivation efficiency achieves 92% within 90 min under visible light irradiation. This work may shed new light on designing highly-efficient photocatalysts with multiple defects. [ABSTRACT FROM AUTHOR]

• Benzoquinone (BQ) promoted the heterogeneous process of PMS activation by Fe 3 S 4. • Degradation and mineralization of bisphenol A (BPA) were enhanced when BQ was injected into Fe 3 S 4 /PMS system. • PMS and BQ were activated to active complexes (BQ-PMS*) on the surface of Fe 3 S 4. • BPA would be directly oxidized by BQ-PMS*. Benzoquinone (BQ) is of great significance for enhancement of contaminants degradation in the homogeneous oxidation system of peroxymonosulfate (PMS). However, the role of BQ in the heterogeneous activation of PMS for contaminants oxidation is still not clear. Herein, this work reported that the addition of BQ into the Fe 3 S 4 /PMS system could effectively enhance the degradation and mineralization of bisphenol A (BPA). Mechanistic study uncovered that the BQ and PMS would form active complexes (BQ-PMS*) on the surface of Fe 3 S 4 and the excited BQ-PMS* can oxidize the BPA. To be specific, the electron of BPA was extracted by BQ-PMS* and then transfer to the surface of Fe 3 S 4. The surface electron can induce the change of valence state of S and Fe elements, which can trigger the degradation of BPA and inhibit the decomposition of BQ itself. To the best of our knowledge, it is the first time to unveil the positive role of BQ in the heterogeneous activation of PMS, which may shed new light on the establishment of high-efficient PMS-based oxidation technology for remediation of organic pollutant. [Display omitted] [ABSTRACT FROM AUTHOR]

The simultaneous removal of nitrate and bisphenol A (BPA), two highly concerning contaminants in fluvial systems, is limited due to the low activity of the denitrifying community and poor degradability of BPA. Iron-loaded biochars (FeBCs) are efficient in promoting electron transfer efficiency and accelerating redox active processes, e.g., nitrate reduction and pollutant degradation. Nevertheless, the physicochemical properties of FeBCs and their potential strengthening mechanism during simultaneous removal of nitrate and BPA from aquatic systems are largely unknown. This study explored the potential of FeBCs to accelerate the simultaneous removal of nitrate and BPA. The FeBCs were prepared at 300–700 °C, with a BET surface area that increased from 10.78 to 207.97 m2 g−1 and oxygen content that decreased from 12.16% to 3.89%. Maximum nitrate and BPA removal of 99.0% and 74.1%, respectively, was achieved when the biochar was pyrolyzed at 500 °C (FeBC5). FeBC5 increased the levels of nicotinamide adenine dinucleotide (NADH), 5′-adenylate triphosphate (ATP), and electron transport system activity (ETSA) of the microbes, which were 485.50%, 371.88%, and 68.85% higher than the control values. After adding 0.05 g L−1 FeBC, the denitrifying enzyme activity and the level of nitrate-reducing genes increased by 48.22% and 45.6% respectively, and the genera responsible for denitrification and BPA degradation were increased by 5.56% and 33.33%, respectively. The BPA degradation pathway analysis suggested that the enhanced biotransformation of BPA resulted from co-metabolic degradation by denitrifying bacteria. The ferric-containing functional groups and their types were significantly correlated with nitrate-reducing enzymes and metabolic activities, facilitating the simultaneous removal of nitrate and BPA. [Display omitted] • FeBC5 exhibits an abundance on diverse forms of iron and redox-active functional groups. • FeBC5 performs best in improving electron transfer efficiency of microbes. • FeBC5 significantly enhances enzymatic activity and microbial metabolism. • Mechanism of simultaneous BPA biodegradation and nitrate reduction is revealed. • FeBCs promote co-metabolic degradation of BPA under denitrifying condition. [ABSTRACT FROM AUTHOR]

Layered montmorillonite with abundant hydroxyl groups was employed as a supporting matrix to anchored oxygen vacancy-rich Co 1.3 Mn 1.7 O 4 nanoparticles (CM/Mt) for environmental remediation. The optimal CM/Mt. composite could efficiently degrade bisphenol A (BPA) in the presence of peroxymonosulfate to exhibit the highest degradation efficiency of 98% within 21 min, which was about 1.4-fold higher than that of pristine Co 1.3 Mn 1.7 O 4 nanoparticles. The junction of montmorillonite and Co 1.3 Mn 1.7 O 4 nanoparticles boosts the specific surface area and provides more hydroxyl anchored sites by effectively reducing the grain size and agglomeration of Co 1.3 Mn 1.7 O 4 , which was conducive to the enrichment of pollutants and provides sufficient active sites for the degradation reaction. The liquid chromatogram and mass spectra were adopted to characterize the intermediates and degradation routes for the BPA degradation process. Radical quenching and EPR results confirm that the 1O 2 was the dominant active species in the oxidation process, which benefited from the existence of abundant oxygen vacancies in the CM/Mt. composite. This work not only provides a new high-efficiency clay-based catalyst for PMS activation, but also explores a kind of high value-added product of montmorillonite. • Bentonite-supported Co 1.3 Mn 1.7 O 4 (CM/B-60) can efficiently activate PMS for bisphenol A removal. • The 1O 2 acted as the dominant active species during the degradation process. • Junction of bentionite and Co 1.3 Mn 1.7 O 4 provides more active sites for PMS activation. [ABSTRACT FROM AUTHOR]

Photocatalytic nitrogen fixation combined with degradation of organic pollutants is a promising technology to alleviate the growing energy and environmental crisis. In this work, Ti 3 C 2 T x /CuZnInS (TiC/CZIS) Schottky heterojunction difunctional photocatalytic was rationally designed for efficient nitrogen fixation synergistic bisphenol A (BPA) degradation. The Ti 3 C 2 T x ultra-thin nanosheets with richer surface-active groups and lower Fermi level greatly improved the carrier generation and separation ability of CZIS nanosphere. In addition, the coupling of TiC extended the absorption of CZIS to infrared region, which provided the possibility of efficient photocatalytic activity in cloudy and rainy days. As a result, an enhanced photocatalytic nitrogen fixation activity of 45.6 μmol/g/h was achieved. It should be noted that once appropriate amount of BPA was introduced to the photocatalytic system, a satisfied activity of 82.5 μmol/g/h was obtained, BPA can also be degraded by 58.5% within 180 min by TiC/CZIS. Through a series of experimental characterizations, the photocatalytic active substances and degradation pathway of BPA was investigated, and the possible photocatalytic mechanism was established. This work lays a foundation for the design of environmentally friendly photocatalysts and their applications in the fields of environmental purification and energy conversion. [Display omitted] • Ti 3 C 2 T x decorated CuZnInS was designed for waste to energy conversion. • The hybrid has richer reactive sites, enhanced charge transfer and sunlight response ability. • Enhanced nitrogen fixation activity is achieved by the assistance of BPA. • A systematic study of photocatalytic mechanism was proposed. [ABSTRACT FROM AUTHOR]

Bioelectrochemical systems (BESs) with integrated photoactive components have been shown to be a promising strategy for enhancing the performance for bioenergy generation and pollutant removal. This study revealed an efficient photo-BES with an enhanced pollutant degradation rate by utilizing self-produced biomolecules as photosensitizers in situ. Results showed that the BES could increase the coulombic efficiency from 60.8% to 73.0% and the degradation rate of bisphenol A (BPA) from 0.030 to 0.189 h−1 when the suspension in the reactor was illuminated with simulated sunlight in the absence of any external photosensitizers. We identified that the regular BES released many organic substances into the reactor during operation. These substances, including dissolved biomolecules and solid cell residues, were photoactive for producing hydroxyl radicals during light illumination. Quenching experiments verified that the •OH generated from the self-produced biophotosensitizers contributed to the enhanced degradation of BPA. Additionally, the phototransformation of biophotosensitizers was also observed in photo-BES. The quantity of tyrosine protein-like components decreased, but that of the humic components remained relatively stable. Our findings imply that BESs with integrated self-produced biophotosensitizers may be promising for constructing advanced electrochemical and biological systems for synchronous bioelectricity production and degradation of organic pollutants in wastewater treatments. [Display omitted] • BES integrated with illumination to develop a photo-BES for pollutants degradation. • Photo-BES induced photochemical effect by self-produced biophotosensitizer. • BPA degradation rate of photo-BES was 6 times higher than that of without sunlight. • Biophotosensitizers could be photoactivated to generate •OH free radicals. • Photo-BES as a potential way to high-efficiently remove pollutants in wastewater. [ABSTRACT FROM AUTHOR]

[Display omitted] • Mycogenic synthesis and characterization of manganese nanoparticles (AGE-Mn NPs) • The size of the Mn NPs was < 200 nm with a zeta potential of −8.72 ± 0.96 mV. • AGE-Mn NPs significantly inhibited the growth of the bacterial pathogen E. coli. • Mn NPs photocatalytically degraded about 66.3 % of bisphenol A. • The photocatalytically degraded BPA did not show any toxicity to brain shrimp larvae. The present study aimed to synthesize manganese nanoparticles (Mn NPs) using endophytic fungi (Arcopilus globulus strain KNUEP5). The Arcopilus globulus extracts (AGE) mediated manganese nanoparticles (AGE-Mn NPs) were characterized using various materials characterization equipment, including UV–vis spectrophotometer, TEM-EDS, FTIR, and XRD. The characterization results showed an intense absorption peak at 324 nm in the UV spectrum, which indicates the successful synthesis of AGE-Mn NPs. AGE-Mn NPs were found to be spherical with a size of < 200 nm as indicated by TEM analysis. AGE-Mn NPs exhibited a zeta potential size of 130.2 ± 23.69 nm with a zeta potential of −8.72 ± 0.96 mV. FTIR analysis indicated the involvement of the various functional molecules in the AGE to the synthesis of the AGE-Mn NPs. Further, XRD results proved the crystalline structure of AGE-Mn NPs. The antibacterial and CLSM assays revealed that the AGE-Mn NPs significantly inhibited the bacterial pathogen (Escherichia coli). In addition, AGE-Mn NPs were very good at triggering the photocatalytic degradation of BPA, which made it less toxic to brine shrimp larvae. [ABSTRACT FROM AUTHOR]

Bio-degradation with laccase immobilized on the TiO 2 functionalized membrane offers an attractive option to augment the conventional wastewater treatment processes for the removal of micropollutants such as Bisphenol A (BPA). Immobilization of the enzyme on nanostructured TiO 2 coated membranes addresses the common issues such as the poor activity and stability associated with the free laccase, as well as reducing the loss of laccase. Furthermore, the removal of large molecular weight BPA degradation products presents another benefit with this bio-catalytic membrane system. In this work, the TiO 2 nanoparticles were coated on the membrane surface via a low temperature hydrothermal sol–gel process, and the laccase was subsequently immobilized on these membranes by chemical coupling. The PVDF membranes with different pore sizes (0.1 and 0.45 µm) and coating cycles (up to 4 cycles) were used to examine the effects of the TiO 2 loadings and the nanostructure of the coating layer on the laccase immobilization performance. The optimal apparent activity and activity recovery were achieved on the 0.1 µm membrane with 3 coating cycles based on the 2,2′-azino-bis-(3-ethyl benzothiazoline-6-sulfonic acid) (ABTS) assay, due to the larger BET surface area and BJH pore diameter observed on this membrane. Substantial improvement in BPA removal efficiency and stability under moderate flux conditions were also obtained on the TiO 2 functionalized membranes, in good agreement with the ABTS assay results. In addition, the polymer products derived from the BPA bio-degradation process showed negligible fouling impact on the coated 0.1 µm membrane. [ABSTRACT FROM AUTHOR]

The slow redox rate of Fe(III)/Fe(II) couples is a rate-limiting step for Fenton-like performance of Fe-MOFs. In this study, a series of catalysts (MIL-101) with various p-phthalic acid/2-aminoterephthalic acid (H 2 BDC/NH 2 –H 2 BDC) molar ratios were prepared using a simple and mild chemical method and applied for catalyzed degradation of bisphenol A (BPA). Interestingly, the –NH 2 modified MIL-101(Fe) can adjust Fe-Oxo node by increasing the electron density of Fe(III) in the presence of –NH 2 group with high electron density, thus forming Fe(II) in situ in MOFs. Meanwhile, the –NH 2 groups used as electron-donors can promote electron transfer, resulting in faster Fe(III)→Fe(II) half-reaction and active H 2 O 2 to continuously generate •OH radical. The BPA degradation and rate constant of Fe-BDC-NH 2 /H 2 O 2 system are 15.4-fold and 86.8-fold higher than that of Fe-BDC/H 2 O 2 system, respectively. The density functional theory (DFT) calculations showed that Fe-BDC-NH 2 possesses higher Fermi level energy (−4.88 eV) and lower activation energy barriers (0.32 eV) compared with Fe-BDC. Moreover, Fe-BDC-NH 2 showed good reusability and stability. This work offers a highly efficient and stable MOFs-based Fenton-like catalyst to rapidly degrade organic pollutants over a wide pH range for potential applications in wastewater treatment. [Display omitted] • Fe-BDC-NH 2 was successfully prepared by a simple and mild chemical method. • The electron of –NH 2 on Fe-BDC-NH 2 in situ reduced Fe(III) to Fe(II). • Amino modification improved Fe(III).→Fe(II) reaction and Fe(III)/Fe(II) cycle. • The rate constant by Fe-BDC-NH 2 was 86.8-fold higher than Fe-BDC system. • The effective pH range was further broadened to 9.0. [ABSTRACT FROM AUTHOR]

[Display omitted] • 2D ultrathin BiO(HCOO) x I 1-x composites were fabricated via a facile solvothermal method. • BiO(HCOO) 0.75 I 0.25 exhibited excellent photoactivity due to the synergistic effect of ultrathin 2D structure and hybrid composite. • Hybrid composite endowed the h+ a higher oxidation potential. • 2D ultrathin structure accelerated charge carriers separated rate by reducing their migration distance. Here, a novel series of 2D BiO(HCOO) x I 1-x composites were first fabricated with a ultrathin thickness (∼2.47 nm). Among them, the optimal BiO(HCOO) 0.75 I 0.25 nanosheets exhibited a superior photocatalytic performance with the kinetic constant reaching up to 0.2148 min−1, which was 5.9, 97.6 and 27.2 folds higher than that of pristine BiOI, BiOCOOH and BiO(HCOO) 0.75 I 0.25 -P nanoplates, respectively. Benefiting from the synergistic effect of ultrathin two-dimensional structure and hybrid composite, the photocatalytic performance was signally improved. Based on the optical and photoelectrochemical characterizations, the fabrication of hybrid composite delivered the optimal balance of visible-light absorption and redox capacity, endowing the photoinduced holes a higher oxidation potential. Meanwhile, the construction of 2D ultrathin structure reduced the migration distance of charge carriers, consequently accelerated those separated rate. This study provides a new insight for designing high active Bi-based photocatalysts, which is hopeful to make a great contribution to aquatic environmental restoration. [ABSTRACT FROM AUTHOR]

At present energy and environmental remediation are of highest priority for the well defined sustainability. Multifunctional materials that solve both the issues are on high demand. In the present work, a simple method has been followed to extract carbon spheres from Tamarindus indica (commonly known astamarind fruit) shelland doped with nitrogen (N-CS). Vanadium pentoxide nanoflakes were decorated aroundN-CS and the resultant is labeled as V 2 O 5 /N-CS nanocomposite. The spectroscopic, microscopic, elemental mapping and x-ray photoelectron spectroscopic characterization confirm the nitrogen doping and formation of hybrid material. N-CS, V 2 O 5 , and V 2 O 5 /N-CS nanocompositehave been evaluated for their efficiency to evolve hydrogen and for degradation of Bisphenol A (BPA) under visible light. In addition, electrocatalytic hydrogen evolution in presence of light has also been evaluated. The DRS spectrum proves the decrease in the bandgap of V 2 O 5 upon its decoration around N-CS material. In a photochemical experiment, the V 2 O 5 /N-CS nanocomposite evolved 18,600 μmolg−1 of H 2. Electrochemical hydrogen evolution has also been evaluated in presence of light and obtained the onset potential of −60mV with 52 mV dec−1 Tafel slope value. Scavenger studies indicate superoxide radicals and hydroxyl radicals are the active species responsible for the degradation of BPA. BPA degradation pathway has been predicted with the support of LC-MS results of the intermediates. All these results indicate the synthesized nanocomposite could be an efficient, stable multifunctional material for photocatalytic applications. [Display omitted] • Carbon spheres synthesis from Tamarindus indica waste shell doped with N. • Decoration of V 2 O 5 nanoflakes around N-CS. • Bandgap reduction in V 2 O 5 /N-CS nanocomposite (1.95 eV). • 95% degradation of BPA under optimized condition. • Discussed the degradation pathway of BPA with the support LC-MS results. [ABSTRACT FROM AUTHOR]

The discharge of recalcitrant and persistent organic pollutants into the environment and subsequent adverse impacts on the ecosystem has aroused a great concern all over the world. In this study, dielectric barrier discharge (DBD) non-thermal plasma was employed to eliminate bisphenol A (BPA). The influences of several vital experimental parameters, including discharge voltage, initial pH of solution, and rate of water flow on degradation of BPA, were explored in detail. In addition, the real wastewater from pharmaceutical factory was utilized to test the oxidation performance of DBD system. 96.8% chemical oxygen demand removal was achieved using DBD system. Radical quenching experiment as well as electron paramagnetic resonance test demonstrated that •OH was the main reactive oxygen species for the degradation of BPA. Moreover, eight major BPA degradation intermediates were identified by UPLC-MS. Ultimately, based on the UPLC-MS test results, a possible degradation pathway of BPA was proposed. [Display omitted] • DBD system was utilized to remove persistent organic pollutants. • BPA degradation efficiency under various experimental conditions is evaluated. • OH was the main ROS for the degradation of BPA. • Mineralization process and a possible degradation pathway was investigated. [ABSTRACT FROM AUTHOR]

Abstract: The degradation of an endocrine disruptor (ED), the bisphenol A (BPA), was studied using Gliding Arc Discharge (GAD). This kind of discharge generates a non-thermal plasma at atmospheric pressure and quasi-ambient temperature. The resulting plasma is the source of several chemical reactions that lead to the hydroxyl radical formation. Hydroxyl radicals, ery powerful and non-selective oxidizing agents ( 2.8V vs. normal hydrogen electrode) able to degrade compounds resistant to conventional treatment. GAD belongs to the group of advanced oxidation processes (AOPs). Under different working gases such as air, argon, oxygen/argon mixture (20/80, v/v), a BPA aqueous solution (120μM) was submitted to GAD. The evolution of BPA concentration was followed by high performance liquid chromatography (HPLC) method. The global oxidation of the organic matter was followed by chemical oxygen demand (COD) measurement. The mineralization was determined from the total organic carbon (TOC). The GAD treatment of the aqueous solution is accompanied by a massive production of hydrogen peroxide. The addition of Fe (II) to the reaction allows a better elimination of the organic matter through the production of additional ls, issued from the decomposition of hydrogen peroxide according to Fenton reaction. The optimized system – GAD with oxygen/argon (20/80) as working gas, in presence of Fe (II) – was very efficient for BPA treatment: the compound disappeared after 30min, the abatement of the COD was total after 120min and the TOC diminished by 70%. [Copyright &y& Elsevier]

In this study, (1) the change in the concentration of bisphenol A (BPA) leached from polycarbonate plastic (PCP) tube to water samples containing phosphate, sodium barbital, glycine, methionine or albumin at 37 °C as a function of time, and (2) the degradation rate of BPA leached from PCP tube to amino acid solutions in the presence of radical oxygen species (ROS) were investigated. The BPA leaching velocity (BPA-LV) from PCP tube to 50 mM glycine at pH 6 or 7 was twice that to control water, and the leaching was enhanced above pH 8. At pH 11, BPA-LV was significantly higher in 50 mM glycine and methionine solutions than in 50 mM NaOH. These results indicate that basic pH and amino acids contained in water could accelerate BPA leaching. The BPA-LV in phosphate buffer was different from the BPA-LVs in other buffers (barbital and glycine) at the same pH. BPA leached to the glycine or methionine solutions at pH 11 was degraded time dependently in a similar manner as the control water in the presence of ROS. The degradation of leached BPA was inhibited in the glycine solution, but was accelerated in the methionine solution. However, degradation of BPA added to freshly prepared methionine was inhibited in a similar manner to BPA in glycine. BPA degradation could be influenced by some kinds of amino acids, but glycine and methionine might be involved in BPA degradation in different ways. [Copyright &y& Elsevier]

In this study, (1) change in the concentration of bisphenol A (BPA) leached from polycarbonate (PC) tube to control water (BPA free), seawater and river water at 20 and 37 °C as a function of time, (2) the fate of BPA caused by addition of H2O2 and Fe3+ to seawater containing BPA leached from PC tube were assessed. BPA leached from PC tube to all water samples increased with the ascendant of temperature and with the passage of time. The BPA leaching velocity in seawater was the fastest in three samples (11 ng/day for seawater, 4.8 ng/day for river water 0.8 ng/day for control water at 37 °C).BPA leaching velocity from PC tube was significantly high at pH 8 (50 mM Na2HPO4) and increased dose-dependently. There was no difference in the velocity of BPA among the 50 mM phosphate-buffers at pH 6.5, 7.0 and 7.5. BPA was leached three times higher by addition of Na+ than K+. However, the higher the K+ concentration, the larger the BPA leached from PC tube. Na+ mixed with PO4− was effective on BPA leaching from PC tube, but not with SO4− or Cl−. The results suggested that BPA leaching from PC tube would be attributed to the concentration of bibasic phosphate such as Na2HPO4 and K2HPO4 in water samples. BPA was degraded in both control water and seawater in the presence of radical oxygen species, but the degradation rate was lower in seawater than in control water, suggesting that anti-oxidative system exists in seawater. Neo-synthesized substance in both control water and seawater in the presence of reactive oxygen species was identified as BPA-quinone by LC–MS. [Copyright &y& Elsevier]

Photocatalysis provides an impetus for the synergetic removal of Cr(VI) and organic contaminants, but the generation of Cr intermediates and their potential oxidizability may be overlooked in pollutant conversion. Herein, the Cr intermediates in the Cr(VI) reduction process were emphasized in Cr(VI)/bisphenol A (BPA) by using graphitic carbon nitride as a photocatalyst. The active species for BPA photodegradation in the BPA system and Cr(VI)/BPA system suggested that the Cr(VI) reduction process indeed promotes BPA photodegradation. Electron paramagnetic resonance (EPR) of Cr complexes and in situ variable-temperature EPR analysis demonstrated Cr(V) intermediate ( g = 1.978) generation in Cr(VI) reduction and its oxidization for BPA degradation in photocatalysis. By adding the electron donor Na 2 SO 3 , BPA degradation was induced in Cr(VI)/BPA solution, further confirming the positive effect of Cr(V). Moreover, the difference in BPA degradation products in the BPA/air, Cr(VI)/BPA/air, and Cr(VI)/BPA/Ar systems indirectly explained why the Cr(V) intermediate was involved in BPA degradation. Density functional theory calculations revealed that photogenerated electrons can reduce the free energy (0.98 eV) of converting Cr(VI) into Cr(V), which can facilitate the subsequent Cr(V) oxidation step for BPA degradation. This work contributes to the exploration of the Cr(VI) reduction process and the synergistic removal of organic pollutants in Cr(VI)/organics systems.

• Bimetallic N-doped carbonaceous nanorods derived from MOFs is synthesized. • A surface reaction mechanism is proposed. • The drawback of short half-life periods of ROS is well overcome. • The effect of reaction parameters for the degradation of BPA is evaluated. Advanced oxidation based on persulfate (PS) activation presents one of the most promising methods to generate reactive oxygen species (ROS) to deal with the increasing environmental contamination. However, the half-life periods of most ROS generated from PS activation are quite short. To this end, using bimetallic amino-functionalized metal-organic frameworks (MOFs) as both a precursor and a template yields functional N-doped carbonaceous hybrid nanorods (FeCo-NC) are synthesized, characterized, and studied. The results demonstrate FeCo-NC600 can effectively dissociate persulfate into ROS to degrade bisphenol A (BPA) in absence of heat and light owing to the well-defined structure and metal coordination provided by pristine MOFs and N-doped carbon network. In the FeCo-NC600/PS system, BPA achieved a complete removal in 20 min with a pseudo-first-order rate constant of 0.2876 min−1, and about 85% of Total Organic Carbon (TOC) removal was observed. In addition, the catalyst can be reused without significant loss in activity. Further studies reveal the contribution of surface bound sulfate radical, surface bound hydroxyl radicals, and singlet oxygen in BPA degradation. Meanwhile, a surface reaction mechanism is proposed, it can achieve the simultaneous generation of ROS on the catalytic site and efficient degradation of BPA on the adsorption site, thereby reducing the migration distance of ROS and excellently overcome the problem of short half-life of ROS, further improving the catalytic activity. [ABSTRACT FROM AUTHOR]