Electron Spin Resonance Investigation Research Articles

Covalent triazine frameworks as particle electrode for three-dimensional photoelectrocatalytic degradation of oxytetracycline: Synergy effects, pathway, and mechanism.

Photoelectrocatalysis has been widely employed for degrading antibiotics due to its high efficiency. However, the application is significantly impeded by the rapid recombination of photogenerated charge carriers and the limited surface areas of photoelectrodes. In the study, high crystallinity covalent triazine frameworks were fabricated at low temperature of 150°C and firstly used as particle photoelectrode in the three-dimensional photoelectrochemical reactor to degrade oxytetracycline (OTC). SEM, TEM, XRD, XPS, and FT-IR confirmed the successful synthesis of high crystallinity covalent triazine frameworks. Compared to CTF-120 (71.2%) and CTF-180 (46.9%), CTF-150 exhibited excellent OTC removal. Electrochemical impedance, UV-vis absorption spectra, and Mott-Schottky tests showed that CTF-150 demonstrated more wide light absorption range of 501nm and narrow bandgap of 2.52eV, and smaller Rct value under illumination, in comparing to CTF-120 and CTF-180. When the initial concentration of OTC was 50mgL-1, the 86.2% of OTC removal and 62.7% of mineralization were obtained under light irradiation (λ>420nm), current of 10mA, pH of 6.4, electrolyte of 0.1M Na2SO4. The synergy effect between photocatalytic and electrocatalytic processes of CTF-150 not only enhanced by 38.5% current efficiency but also reduced energy consumption to 1.90 kWh m-3. CTF-150 had a wide range of acid-base application and displayed resistance on coexisting ions. Electron spin resonance detection, quenching experiments, and probe experiments illustrated that h+, •O2-, 1O2, and •OH contributed to the degradation of OTC and the generation pathways of •O2-, 1O2, and •OH were verified. Moreover, •O2-, 1O2, and h+ were the main reactive species responsible for OTC removal, while 1O2 was for OTC mineralization. Based on high-performance liquid chromatography-tandem mass spectrometry detection, OTC with benzene ring was decomposed to opening ring products. The acute toxicity, developmental toxicity, bioaccumulation factor and mutagenicity of OTC and its intermediates using T.E.S.T. showed the toxicity of 82.35% degradation products decreased.

Simultaneous Quantitation of Persulfides, Biothiols, and Hydrogen Sulfide through Sulfur Exchange Reaction with Trityl Spin Probes.

Reactive sulfur species (RSS) including persulfides (RSSHs), biothiols, and hydrogen sulfide (H2S) are key regulators in various physiological processes. To better understand the symbiotic relationship and interconversion of these RSS, it is highly desirable but challenging to develop analytical techniques that are capable of detecting and quantifying them. Herein, we report the rational design and synthesis of novel trityl-radical-based electron paramagnetic resonance (EPR) probes dubbed CT02-TNB and OX-TNB. CT02-TNB underwent fast sulfur exchange reactions with two reactive RSSHs (PS1 and PS2) which were released from their corresponding donors PSD1 and PSD2 to afford the specific conjugates. The resulting conjugates exhibit characteristic EPR spectra, thus enabling discriminative detection and quantitation of the two RSSHs. Moreover, CT02-TNB showed good response toward other RSS including glutathione (GSH), cysteine (Cys), H2S, and sulfite as well. Importantly, based on the updated EPR spectral simulation program, simultaneous quantitation of multiple RSS (e.g., PS1/GSH/Cys or PS1/GSH/H2S) by CT02-TNB was also achieved. Finally, the levels of released PS1 from PSD1 and endogenous GSH in isolated mouse livers were measured by the hydrophilic OX-TNB. This work represents the first study achieving discriminative and quantitative detection of different persulfides and other RSS by a spectroscopic method.

Mechanistic and DFT studies on the degradation of metronidazole by cerium oxide-loaded iron-cobalt layered double hydroxide-activated calcium sulfite

In this study, Co3Fe-LDHs loaded with CeO2 were synthesized via a hydrothermal method, and the synthesized Co3Fe-LDHs@CeO2 exhibited excellent surface properties and structural stability. Moreover, Co3Fe-LDHs@CeO2 was first applied to activate CaSO3 for metronidazole (MNZ) degradation. The effects of the catalyst preparation ratio, initial pH, and coexisting substances in the system on MNZ degradation were investigated. At an initial pH of 7.0, when 0.2 g/L Co3Fe-LDHs@CeO2 and 2 mM CaSO3 were combined, 99 % of the MNZ at a concentration of 20 mg/L was eliminated in 60 min. The experimental results revealed the rapid activation of CaSO3 on the catalyst surface, where Ce plays a key role in the redox cycle between Co and Fe atoms. The loading of CeO2 enhanced the catalytic performance of Co3Fe-LDHs, as confirmed by density functional theory (DFT) calculations. The loading of Ce promoted the chemisorption of CaSO3 on the surface of Co3Fe-LDHs@CeO2, leading to the transfer of 1.48 electrons from sulfite to Co3Fe-LDHs@CeO2. These findings were consistent with the results of the electrochemical tests. SO4•- and •OH were identified as the primary active substances through electron paramagnetic resonance (EPR) and chemical probe experiments, accounting for 60.73 % and 32.81 %, respectively. By combining LC–MS and DFT calculations, three potential degradation pathways of MNZ were identified, with the intermediates found to be either nontoxic or have low toxicity. Even after being recycled five times, MNZ still showed 88 % degradation, demonstrating its exceptional reusability. Co3Fe-LDHs@CeO2 shows great potential for practical use in treating antibiotic wastewater due to its outstanding catalytic properties, anti-interference ability, reusability, and stability.

Synergetic photocatalytic degradation of the tetracycline antibiotic over S-scheme based BiOBr/CuInS2/WO3 ternary heterojunction photocatalyst

The present research investigated the photodegradation capability of a ternary BiOBr/CuInS2/WO3 heterojunction against the tetracycline (TC) antibiotic. BiOBr/CuInS2/WO3 heterojunction is formed using a straightforward physical mixing method, whereas pure photocatalysts (CuInS2, WO3) were synthesized hydrothermally and BiOBr by a coprecipitation process. The Field Emission Scanning Electron Spectroscopy examination validated the nanorod and nanosheet shape of the fabricated BiOBr-CuInS2-WO3. The photodegradation capabilities of the BiOBr-CuInS2-WO3 heterojunction were superior to those of other pure photocatalysts, and it followed the S-scheme charge transfer route as indicated by the band alignments. After 120 min of light irradiation, the BiOBr/CuInS2/WO3 S-scheme ternary heterojunction obtained a photodegradation rate of 98.9 %, much greater than other pure photocatalysts. According to electron spin resonance investigations and scavenging experiments, the radicals hydroxyl radicals (•OH), hole (h+), superoxide (•O2−) play a significant role in the photodegradation of TC. The ternary heterojunction's improved light absorption, lower recombination rate, and higher photocarrier separation rate were due to the fabrication of S-scheme heterojunction. The ternary BiOBr/CuInS2/WO3 photocatalyst's photodegradation efficacy was consequently enhanced. Investigations for photocatalyst reusability demonstrated its exceptional stability, with a 93.8 % degradation rate after five catalytic cycles.

Quantitative and mechanistic elucidation of the reactive oxygen species for effective sulfamethoxazole removal in heterogeneous peroxymonosulfate activated by MOFs-derived cladding structure CoZn/NC@UiO

In cobalt-based catalyst/peroxymonosulfate (PMS) systems, the key issues are the leaching of metals and the stability of catalysts. In this study, a NH2-UiO-66 cladded CoZn/NC catalyst was synthesized for efficient degradation of sulfamethoxazole (SMX) using activated PMS. The removal efficiency of SMX could achieve 100% within 30 min. The leaching of Co2+ was inhibited to 0.05 ppm and the anti-interference and cyclic stability of the catalyst were enhanced by the NH2-UiO-66 shell. In addition, the quenching experiment, electron paramagnetic resonance (EPR) technique and probe experiment were used to analyze the reactive oxygen species (ROSs) qualitatively and quantitatively. The findings demonstrated that singlet oxygen (1O2) had the highest steady-state and cumulative concentration. However, 1O2 could only participate in the degradation of SMX through single electron transfer or addition reaction, resulting in a lower second-order rate constant of the SMX reaction with 1O2. Sulfate radical (SO4·-) contributed the most to the degradation of SMX due to the high reactivity of the sulfonamide structure in SMX to SO4·-. Finally, possible pathways for SMX degradation were proposed. The two primary mechanisms of SMX degradation were S-N cleavage and amino hydroxylation/oxidation. The toxicity of most of the intermediates was less than that of SMX through ecological structure–activity relationship analysis. Overall, a novel approach to synthesize low leaching and efficient cobalt based catalyst was put forward, and the activation mechanism of PMS was also revealed.

Exploration of sulfamethoxazole removal triggered by copper slag-based geopolymer: Radical versus nonradical contributions

The advanced oxidation processes based on sulfate radicals offer environmental sustainability and exhibit potential for effectively breaking down antibiotics. Among various iron-based materials for activating peroxydisulfate, copper slags are iron-rich raw material and can serve as an excellent catalyst. In this study, acid-activated copper slag-based geopolymers were successfully synthesized using a 1:1 mass ratio of copper slag and metakaolin as raw materials. In the geopolymer based electrocatalytic system, the removal of sulfamethoxazole (SMX) was 99.1 % within 60 mins under the optimized operating conditon of initial pH 3.0, current density of 20 mA/cm2, inter-electrode distance of 3 cm, geopolymer dosage of 1 g/L, and electrolytic concentration of 75 mM/L. The presence of GP provided surface Fe(II) to further activate H2O2 and peroxydisulfate and hence promote the degradation of SMX. Electron paramagnetic resonance spectroscopy, quenching experiments, electrochemical techniques, and probe analysis, were employed to investigate the radical and nonradical pathways within the system. The reactive oxygen species identified in the proposed system included hydroxyl radicals (·OH), sulfate radicals (SO4·-), and singlet oxygen (1O2). SO4·- was the predominant reactive oxygen species, playing a crucial role in the radical pathway with a contribution of 62.1 %. 1O2 was the sole nonradical pathways involved, exerting limit influence on SMX degradation. Additionally, six potential intermediate pathways for SMX degradation were identified. This research not only systematically offers a comprehensive understanding of the oxidation mechanisms in heterogeneous electro-catalytic systems but also demonstrates a high-value utilization strategy of metallurgical industrial solid waste for resource recycling.

Enhanced Degradation of Micropollutants in a Peracetic Acid/Mn(II) System with EDDS: An Investigation of the Role of Mn Species.

Extensive research has been conducted on the utilization of a metal-based catalyst to activate peracetic acid (PAA) for the degradation of micropollutants (MPs) in water. Mn(II) is a commonly employed catalyst for homogeneous advanced oxidation processes (AOPs), but its catalytic performance with PAA is poor. This study showed that the environmentally friendly chelator ethylenediamine-N,N'-disuccinic acid (EDDS) could greatly facilitate the activation of Mn(II) in PAA for complete atrazine (ATZ) degradation. In this process, the EDDS enhanced the catalytic activity of manganese (Mn) and prevented disproportionation of transient Mn species, thus facilitating the decay of PAA and mineralization of ATZ. By employing electron spin resonance detection, quenching and probe tests, and 18O isotope-tracing experiments, the significance of high-valent Mn-oxo species (Mn(V)) in the Mn(II)-EDDS/PAA system was revealed. In particular, the involvement of the Mn(III) species was essential for the formation of Mn(V). Mn(III) species, along with singlet oxygen (1O2) and acetyl(per)oxyl radicals (CH3C(O)O•/CH3C(O)OO•), also contributed partially to ATZ degradation. Mass spectrometry and density functional theory methods were used to study the transformation pathway and mechanism of ATZ. The toxicity assessment of the oxidative products indicated that the toxicity of ATZ decreased after the degradation reaction. Moreover, the system exhibited excellent interference resistance toward various anions and humid acid (HA), and it could selectively degrade multiple MPs.

Efficient decontamination and detoxification of phenols by photocatalytic CQDs@Ag3PO4: Re-insights into the targeted reduction and coupling processes of ·O2– and 1O2

Understanding of 1O2 and ·O2– is still mostly restricted to the oxidation properties for open-ring degradation of pollutants. Here we treated the P-nitrophenol (PNP) with toxic and antioxidant nitro group as the targeted pollutant with the prepared carbon quantum dots-modified silver phosphate (CQDs@Ag3PO4) photocatalyst. Quenching experiments, electron paramagnetic resonance spectroscopy characterizations, probe experiments, and comparative tests on TOC removal have confirmed photoinduced holes (h+), singlet oxygen (1O2) and superoxide anion (·O2–) induced by photogenerated electrons and molecular oxygen are the primary reactive species involved in the aerobic system. Through targeted experiments in the Xanthine/XOD and NaClO/H2O2 systems HPLC-MS and Fukui Function, it reveals the targeted reduction of ·O2– and coupling role of 1O2 and their synergistic effect on decontamination and detoxification of PNP. Moreover, the replacement of ring-opening degradation with oligomerization by 1O2 induced follows a new carbon transfer pathway. Accordingly, four PNP elimination pathways were proposed, and the key intermediates had low toxicity predicted by T.E.S.T. software, including the oligomers via coupling reaction. Conclusively, this work provides a comprehensive view of 1O2 and ·O2– and proposes an efficient strategy for realizing pollutant control by manipulating reactive species with solar energy utilization.

Ratiometric paramagnetic probe based on ABTS•+ and Mn2+ for detection of glutathione and revelation of the mechanism for MnO2 nanosheet induced oxidation of ABTS

We designed a ratiometric paramagnetic probe based on electron spin resonance (ESR) signals of ABTS radical (ABTS•+) and Mn2+. Two ESR signals from different paramagnetic species (ABTS•+ and Mn2+) coexisting in the same solution were measured at the same time and were present in one spectrum. MnO2 nanosheets with oxidase-like properties were synthesized. The probe was used to investigate the oxidation mechanism of ABTS by MnO2 nanosheets. On one hand, MnO2 nanosheets catalyzed the generation of O2•− which oxidized ABTS to ABTS•+, and on the other hand, a small amount of ABTS was directly oxidized to ABTS•+ by MnO2 which was reduced to Mn2+. Glutathione (GSH) underwent a redox reaction with MnO2 nanosheets to yield Mn2+ with stable ESR signal. The concentration of MnO2 decreased in the presence of GSH, which inhibited the production of O2•− and ABTS•+. As a result, as the concentration of GSH increased, ESR signal of ABTS•+ descended and on the contrary ESR signal of Mn2+ ascended. Accordingly, the signal ratio of ABTS•+ to Mn2+ decreased with the increase of GSH concentration. The proposed ratiometric ESR probe could reduce the influence from background signal and improve the accuracy and sensitivity of the detection. We applied this strategy to the determination of GSH in human erythrocyte cells, and the results showed recoveries between 90.9 % and 92.6 %. With this method, simultaneously monitoring both nanozyme and its chromogenic substrate could be realized and thus a better understand of the mechanism for the function of MnO2 nanomaterial could be achieved.

Highly selective oxidation of 3,7-dichloro-8-dichloro methyl quinoline toward quinclorac by CoPc-Mn-Br catalytic system

Nowadays, the use of quinoline derived synthons as precursors of quinclorac products is an important research topic in green chemistry. O2 is a cheap, stable, and eco-friendly oxidant, holding promise for organic oxidation reactions. Herein, we have pioneered the discovery of CoPc-Mn(OAc)2-HBr (CoPc-Mn-Br) catalyst system for the selective oxidation of 3,7-dichloro-8-dichloro methyl quinoline (3,7-D-8-DMQ) into quinclorac with high 3,7-D-8-DMQ conversion at 59.3 %. The CoPc-Mn-Br exhibits excellent selectivity of quinclorac (up to 60.3 %), affording high quinclorac yield of 35.7 %, which is 3.1-fold higher than the yield of Co(OAc)2-Mn(OAc)2-HBr (Co-Mn-Br). Electron paramagnetic resonance (EPR) investigations and density functional theory (DFT) calculations indicate that CoPc promotes the adsorption and activation of O2 in this oxidation process, which generates more Co3+, leading to producing the reactive intermediate species 3,7-dichloro-8-carbonyl quinoline free radicals via the radical process. The insight achieved from this fundamental study may be further applied to other organic syntheses via selective oxidation.

Crystallinity modulation and microenvironment engineering synergistically manipulate ROS generation on Ni single-atom photocatalysts

The microenvironment modulation of metal-based catalysis sites plays a critical role in single-atom photocatalysis, and remains a grand challenge yet. Herein, the single-atom Ni anchored crystalline carbon nitride (Ni/CCN) nanowire arrays are reported. The obtained Ni/CCN nanowire arrays exhibit an impressive photocatalytic activity (>96% degradation of pharmaceuticals and personal care products (PPCPs) in only 5 min) and photocatalytic rate (maximum 0.5941 min−1) with only clean solar energy input. The Ni/CCN catalyst attached on microfiltration membrane in the continuous flow experiments exhibits >90% PPCPs degradation efficiency over 10 h, demonstrating the ultrahigh activity and long-term operation of the Ni/CCN catalysts. The results of electron spin resonance analysis, probe experiment and theoretical calculations demonstrate that the promoted generation of reactive oxygen species (ROS) highly relies on the crystallinity regulation and microenvironment engineering of active metal sites, which are consequently utilized to trigger the rapid degradation of PPCPs. The introduced Ni-N4 moiety disrupts the uniform distribution of delocalized electrons and precisely tunes the electronic distribution of the microenvironment in CCN, providing an electron-rich region coupled with strong electron transfer effect between Ni and adsorbed O, thus optimizing the crucial step for molecular oxygen activation. This work offers a new idea of photocatalysis from theoretical design towards broad applications through the perspective about modulating microenvironment of active metal sites and optimizing intrinsic electronic properties.

Construction of novel BiOI/CuInS2/ZnO dual S-scheme charge transfer pathway for efficient antibiotic degradation

The present work explored the photocatalytic activity of BiOI–CuInS2–ZnO ternary heterojunction for the photodegradation of the tetracycline (TCl). The bare photocatalysts were prepared via hydrothermal method while the ternary heterojunction was synthesized using simple physical mixing route. The ternary heterojunction of BiOI, CuInS2 and ZnO followed the S-scheme charge transfer pathway exhibiting superior photodegradation ability compared to other synthesized photocatalysts. The attained degradation efficiency of BiOI–CuInS2–ZnO S-scheme ternary heterojunction was 96.75 % within 90 min of light illumination which was much higher than other photocatalysts. Electron spin resonance (ESR) investigations and scavenging experiment indicated that •O2−, and •OH radicals plays an important role in photodegradation of TCl. Furthermore, the structural analysis of synthesized bare photocatalysts was also done via density functional theory (DFT) calculations. The results showed that after the formation of S-scheme heterojunction, the ternary heterojunction showed lower recombination rate (validated via PL analysis) with boosted charge carriers separation rate (confirmed through EIS and TPR analysis) and light absorption ability. This had led to upgradation in photodegradation efficiency of ternary BiOI–CuInS2–ZnO photocatalyst. The reusability test of the photocatalysts confirmed excellent stability of ternary photocatalysts with 90.25 % degradation rate up to five catalytic cycles.

In situ redox growth of Pd/CuOx for enhanced electrocatalytic degradation of organic chlorides via indirect atomic H* reduction

Efficient utilization of atomic hydrogen (H*) is crucial for electrocatalytic dechlorination. We synthesized a Pd/CuOx cathode by atomic reconstruction to boost H* utilization, creating additional active sites within a biphasic interface. This enhanced H* generation degraded 2,4-dichlorophenoxyacetic acid (2,4-D) with a 96 % removal efficiency at 4 mA cm2 and 1.96 kWh m3 energy consumption. Cyclic voltammetry (CV) showed a 0.009 μmol cm2 increase H* on the Pd/CuOx cathode compared to the pristine Cu cathode. The contribution of H* to the electrocatalytic dechlorination process was further corroborated by scavenging experiments and electron spin resonance investigation. We then evaluated the toxicity of products during the degradation process. Density functional theory calculations revealed that the coordination structure between CuOx and Pd optimized the dissociation of H2O and the free adsorption energy of hydrogen. This research introduces an effective alternative to enhance the H* production for the removal of organochlorine compounds from wastewater.

Tumor Targeting with Apatinib-loaded Nanoparticles and Sonodynamic Combined Therapy.

This study implies the enhancement of apatinib killing effect in 4T1 tumor cells through constructing drug-loaded nanoparticles apatinib/Ce6@ZIF- 8@Membranes (aCZM) to enhance tumor therapeutic targeting and reduce toxic side following sonodynamic therapy (SDT). apatinib/Ce6@ZIF-8 (aCZ) were synthesized by in situ encapsulation, and aCZM were constructed by encapsulating the nanoparticles with extracted breast cancer 4T1 cell membranes. aCZM were characterized and tested for the stability by electron microscopy, and the membrane proteins on the nanoparticles' surface were assessed using SDS-PAGE gel electrophoresis. The cell viability of 4T1 cells following treatment with aCZM was tested using cell counting kit-8 (CCK-8). The uptake of nanoparticles was detected by laser confocal microscopy and flow cytometry, and the SDT-mediated production of reactive oxygen species (ROS) was verified by singlet oxygen sensor green (SOSG), electron spin resonance (ESR), and DCFH-DA fluorescent probes. The CCK-8 assay and flow cytometry using Calcein/PI were used to assess the antitumoral effect of aCZM nanoparticles under SDT. The biosafety of aCZM was further verified in vitro and in vivo using the hemolysis assay, routine blood test and H&E staining of vital organs in Balb/c mice. aCZM with an average particle size of about 210.26 nm were successfully synthesized. The results of the SDS-PAGE gel electrophoresis experiment showed that aCZM have a band similar to that of pure cell membrane proteins. The CCK-8 assay demonstrated the absence of effects on cell viability at a low concentration range, and the relative cell survival rate reached more than 95%. Laser confocal microscopy and flow cytometry analysis showed that aCZM treated group has the strongest fluorescence and the highest cellular uptake of nanoparticles. SOSG, ESR, and DCFH-DA fluorescent probes all indicated that the aCZM + SDT treated group has the highest ROS production. The CCK-8 assay also showed that when the ultrasound intensity was fixed at 0.5 W/cm2, the relative cell survival rates in the medium concentration group (10 μg/ml) (5.54 ± 1.26%) and the high concentration group (20 μg/ml) (2.14 ± 1.63%) were significantly lower than those in the low concentration group (5 μg/ml) (53.40 ± 4.25%). Moreover, there was a concentration and intensity dependence associated with the cellkilling effect. The mortality rate of the aCZM in the ultrasound group (44.95 ± 3.03%) was significantly higher than that of the non-ultrasound (17.00 ± 2.26%) group and aCZ + SDT group (24.85 ± 3.08%) (P<0.0001). The live and dead cells' staining (Calcein/PI) also supported this result. Finally, in vitro hemolysis test at 4 and 24 hours showed that the hemolysis rate of the highest concentration group was less than 1%. The blood routine, biochemistry, and H&E staining results of major organs in Balb/c mice undergoing nano-treatments showed no obvious functional abnormalities and tissue damage in 30 days. In this study, a multifunctional bionic drug delivery nanoparticles (aCZM) system with good biosafety and compatibility in response to acoustic dynamics was successfully constructed and characterized. This system enhanced apatinib killing effect on tumor cells and reduced toxic side effects under SDT.

ESR and optical investigation of tetragonal PbTiO3 nanoparticles embedded in lithium tetraborate glass matrix

Glass-nanocomposites (GNCs) samples of composition [(100−x) Li2B4O7–xPbTiO3] with x = 5, 10, 15 and 20 mol% were prepared by melt quenching method. The two phases of the GNCs samples, a glassy phase and PbTiO3 nanoparticles/clusters phase, can be seen in the energy dispersive X-ray spectra and scanning electron microscopic micrographs. Fourier transformation infrared spectra of the GNCs samples exhibited bands due to triangular with NBO’s and tetrahedral borate groups. Additionally, the Ti4+ ions exist in both TiO4 and TiO6 structural units while the Ti3+ ions exist in TiO6 structural units. The electron spin resonance (ESR) spectra of the GNCs samples exhibit two ESR signals, broad and narrow, corresponding to the Ti3+ (3d1) ions in both tetragonal deformed octahedral and in the other structural configuration, respectively. The optical transmission spectra of the GNCs samples exhibited three transmission bands, 3Γ5 → 2Γ3, 2B2g → 2B1g and 2B2g → 2A1g transitions, in the visible region. The variation in optical band gap (Eopt) with increasing PbTiO3 content were due to the conversion between BO3 with NBOs and BO4 units as well as the reduction of Ti4+ to Ti3+ ions in the GNCs matrix. These results demonstrate that the present GNCs may be used for practical applications such as optical devices.

Investigation of the photolysis process of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) and polystyrene (PS) microplastics: Plastics aging effect, transformation products and toxicity assessment

Microplastics (MPs) and persistent pollutants (POPs) are new pollutants that are extensively studied worldwide. To fill the gaps that the degradation processes and mechanisms of polycyclic aromatic hydrocarbons (PAHs) on the surface of most MPs are still unclear, the photochemical transformation of benzo(a)anthracene (BaA) on polyvinyl chloride (PVC) MPs and polystyrene (PS) MPs in water were investigated and compared. The photolysis of BaA on the surface of PS in water proceeded easier than that on PVC within the 48 h irradiation period, with the pseudo-first-order rate constant of 0.0489 min−1 and 0.0181 min−1, respectively, which can be ascribed to the smaller particle size and more OH production of PS MPs. Due to the light competition between the chromophore and BaA as well as the light-shielding effect, aged MPs showed an inhibitory effect on the degradation of BaA compared with pristine MPs. For BaA/PVC MPs system, the degradation of BaA in real water was not significantly affected by coexisting ions and humic acid (HA) (p < 0.05), while slight inhibitory effect on the degradation of BaA appeared for PS MPs in different water matrices (UP: 86.97 %, YR: 84.47 %, PR: 81.42 % and HR: 83.21 %). According to the electron paramagnetic resonance (EPR) test, quenching experiment and probe experiment, the relative contribution of direct photolysis (PVC: 82.02 %; PS: 69.54 %) and indirect photolysis (PVC: 17.98 %; PS: 30.46 %) was confirmed. A total of 14 products were identified, and the product types were not affected by plastics aging. The results of the toxicity assessment indicated that although some intermediate products remained toxic to aquatic organisms, the toxicity of most products was lower than that of BaA. This study provides new insights into the environmental fate of PAHs and the role of MPs in the photolysis process of contaminants in surface water.

Facet and dual vacancy engineering-boosting BiOBr for enhanced CO2 and epoxide cycloaddition reaction under mild and cocatalyst-free conditions: Double substrate active sites and activated surface bromine ions synergy

Among the many strategies for CO2 resource utilization, the synthetic technology of cyclic carbonates with 100 % atom economy through CO2and epoxide is one of the most industrially viable routes, but its efficiency has been severely hampered by the lack of highly active catalytic sites. Moreover, due to the intrinsic thermodynamic stability and kinetic inertia of CO2 and the higher energy barrier of the ring-opening reaction of epoxides, the heterogeneous catalytic conversion of CO2 highly depends on harsh operating conditions, high temperatures and pressures, and the incorporation of cocatalysts. The development of efficient heterogeneous catalysts for CO2 conversion under cocatalyst-free and mild conditions has always been a challenge. Herein, we have proposed a synergetic strategy of facet and vacancy engineering for the construction of highly efficient heterogeneous catalyst BiO1-xBr1-y-(010) for CO2 cycloaddition, where introducing the OVs-BrVs pairs into typical (010) facets BiOBr with simultaneous surface Lewis acid sites Bi3+ and nucleophilic sites Br−. By combining theoretical calculations and a series of systematic experiments, such as CO2 temperature-programmed desorption, electron paramagnetic resonance and fluorescence probe analysis experiments, the introduced OVs-BrVs pair can not only form Bi3+-Bi(3-x)+ dual active sites on the surface, which activate PO and CO2 respectively to reduce the energy barrier of CO2 insertion, but also activate Br− near BrVs to enhance their nucleophilic attacking ability and reduce the energy barrier of epoxides ring-opening. As a result, the BiO1-xBr1-y-(010) with abundant surface OVs-BrVs pairs showed a high cyclic carbonates conversion of 99 % with 100 % selectivity under cocatalyst-free and mild conditions, far surpassing most heterogeneous catalytic systems. This work provides a completely new strategy to construct high-performance heterogeneous CO2 cycloaddition catalysts through a simple facet and vacancy engineering strategy to overcome the harsh operating conditions limitation and the use of cocatalysts.

Effective Degradation of Metronidazole through Electrochemical Activation of Peroxymonosulfate: Mechanistic Insights and Implications

The investigation into the degradation of metronidazole (MNZ), a frequently employed antibiotic, through the electrochemical activation of peroxymonosulfate (PMS) utilizing either boron-doped diamond (BDD) or dimensional stable anode (DSA) as the anode, was conducted in a systematic manner. The enhancement of MNZ removal was observed with increasing current density, PMS dosage, and initial pH. Response surface methodology (RSM), based on a Box–Benken design, was utilized to evaluate the efficiency of MNZ elimination concerning current density (ranging from 11.1 to 33.3 mA/cm2), initial pH (ranging from 3 to 9), PMS dosage (ranging from 1 to 5 mmol·L−1), and reaction time (ranging from 25 to 45 min). The optimal operational conditions for MNZ removal were determined as follows: a current density of 13.3 mA/cm2, a pH of 3.7, a PMS dosage of 2.4 mmol·L−1, and a reaction time of 40 min. Electron paramagnetic resonance (EPR), quenching experiments, and chemical probe experiments confirmed the involvement of •OH, SO4•− and 1O2 radicals as the primary reactive species in MNZ degradation. The presence of HCO3− and H2PO4− hindered MNZ removal, whereas the presence of Cl− accelerated it. The degradation pathways of MNZ were elucidated by identifying intermediates and assessing their toxicity. Additionally, the removal efficiencies of other organic pollutants, such as sulfamethoxazole (SMX), carbamazepine (CBZ), and nitrobenzene (NB), were compared. This study contributes to a comprehensive understanding of MNZ degradation efficiency, mechanisms, and pathways through electrochemical activation of PMS employing BDD or DSA anodes, thereby offering valuable insights for the selection of wastewater treatment systems.

Efficient removal of size-fractionated antibiotic resistance genes (ARGs) in WWTPs secondary effluent by vacuum ultraviolet (VUV) activated potassium peroxymonosulfate (PMS)

Antibiotic resistance genes (ARGs) and mobile genetic elements (MGEs) in secondary effluent from wastewater treatment plants (WWTPs) have a size-fractionated character and conventional processes have difficulties in removing ARGs and MGEs. Therefore, this study aimed to explore the removal efficiency, removal mechanism and regeneration potential of size-fractionated ARGs and MGEs by vacuum ultraviolet (VUV)-activated peroxymonosulfate (PMS) and ascertain their potential hosts in secondary effluent. The proportion of particle-associated (PA)-ARGs and PA-MGEs was 85.07 %, followed by free-living (FL) fraction (14.91 %) and cell-free (CF) fraction (0.02 %). More than 95.00 %∼99.99 % of ARGs and MGEs in PA- and CF- fractions were removed by VUV/PMS, but the average removal efficiency of FL-ARGs and FL-MGEs was 66.15 %. Compared to the regeneration potential of PA- and CF-ARGs and MGEs (0.02 < C/C0 < 5.27), the regeneration occurred mainly in FL-ARGs and FL-MGEs (0.08 < C/C0 < 24.06). ·OH was the dominant radical (16.810 × 10-6 mol/L) in VUV/PMS for the removal of size-fractionated ARGs and MGEs from the secondary effluent, while SO4-· (4.478 × 10-6 mol/L) played a supporting role in the system based on the quenching experiment, electron paramagnetic resonance spectrometer and probe experiments. Based on full-scale classification, conditionally rare or abundant taxa (CRAT) were the core potential hosts in PA-, FL- and CF- fractions, while rare taxa (RT) and conditionally rare taxa (CRT) potential hosts were more diverse in the three fractions. This study suggests that VUV/PMS can effectively remove size-fractionated ARGs and MGEs from secondary effluent and thereby obviously reduce their dissemination risk to receiving water bodies, providing technical support for the engineering application of VUV/PMS in full-scale WWTPs.

Natural air diffusion electrode modified with metal-organic frameworks derived Fe doped porous carbon for sulfamethazine degradation by heterogeneous electro-Fenton

A novel and efficient heterogeneous electro-Fenton process has been developed, utilizing a modified natural air diffusion electrode (NADE) as a bifunctional cathode. This cathode is based on Fe-doped porous carbon (Fe-PC(800)), which is derived from metal-organic frameworks (MOFs). This cathode has the unique ability to simultaneously generate and activate H2O2 in-situ without the need for aeration. Fe-PC(800) synthesized at a pyrolysis temperature of 800 °C exhibited the optimal catalytic efficiency for sulfamethazine (SMT) degradation over a wide pH between 3 and 11, attributed to the production of Fe0 and Fe3C which improved electron transfer efficiency. The presence of Fe0 facilitated the regeneration of Fe2+ and thus increased the activity of the bifunctional cathode in the Hetero-EF process. The co-action mechanism of •OH and 1O2 was confirmed by the radical quenching and electron paramagnetic resonance (EPR) investigations. NADE modified with Fe-PC(800) demonstrated broad applicability towards diverse contaminants and exceptional stability in ten consecutive cycling experiments. This study shed light on the viability of a straightforward and economically viable cathode utilizing NADE without the need of aeration in a Hetero-EF system, offering novel perspectives on bifunctional electrode design and the activation mechanism involving in-situ production and catalysis of H2O2.