Electron Paramagnetic Resonance Analysis Research Articles

Walnut Shell Biomass Triggered Formation of Fe3C-Biochar Composite for Removal of Diclofenac by Activating Percarbonate

Percarbonate (SPC) as a promising substitute for liquid H2O2 has many advantages in the application of in situ chemical oxidation (ISCO). Developing efficient, cost effective and environmentally friendly catalysts for SPC activation plays the key role in promoting the development of SPC-based ISCO. Herein, the walnut shell biomass was combined with ferric nitrate for the catalytic synthesis of Fe3C@biochar composite (Fe3C@WSB), which demonstrated high efficiency in activating SPC for the removal of diclofenac (DCF). The Fe3C showed average crystallite size of 32.6 nm and the composite Fe3C@WSB demonstrated strong adsorptivity. The prepared Fe3C@WSB could activate both SPC and H2O2 with high efficiency at ca. pH 3 with extremely low leaching of iron, while in a weak acidic condition, higher efficiency of DCF removal was obtained in the Fe3C@WSB/SPC process than in the Fe3C@WSB/H2O2 process. Moreover, the Fe3C@WSB/SPC and Fe3C@WSB/H2O2 processes did not show significant differences when supplied with varying amounts of catalyst or oxidant, but the Fe3C@WSB/SPC process exhibited stronger capability in dealing with relatively highly concentrated DCF solution. Based on quenching experiments and electron spin resonance (ESR) analysis, heterogeneous activation of SPC was assumed as the dominant route for DCF degradation, and both the oxidation by radicals, including •OH, •O2− and CO3•−, combined with electron transfer pathway contributed to DCF degradation in the Fe3C@WSB/SPC process. The cycling experiment results also revealed the stability of Fe3C@WSB. This work may cast some light on the development of efficient catalysts for the activation of SPC.

Revealing the vital role of sulfur site on the surface of pyrite in 1O2 formation for promoting ciprofloxacin degradation via peracetic acid activation

Pyrite has been widely utilized to activate oxidants for water treatment, yet the regulation of reactive oxygen species (ROS) by sulfur sites on its surface has been overlooked. In this study, the surface sulfur sites were regulated by thermal modification of natural pyrite in the N2 atmosphere (denoted as P-X, where X represented pyrolysis temperatures ranging from 400 to 700 °C), and these modified pyrites were employed to activate peracetic acid (PAA) for ciprofloxacin (CIP) degradation. The results revealed that the degradation rate of CIP increased as the reduced sulfur content increased, with the P600/PAA system achieving the highest apparent degradation rate (kobs=0.0999 min-1). Quenching experiments and electron paramagnetic resonance (EPR) analysis identified various ROS involved in the P-X/PAA system, with hydroxyl radical (·OH) and singlet oxygen (1O2) identified as dominant reactive species responsible for CIP degradation. The reduced sulfur sites served as the primary active sites facilitating the conversion of organic radicals (·CH3C(O)OO) into superoxide radicals (·O2-) and 1O2. Furthermore, the P600/PAA system demonstrated robust adaptability under both acidic and neutral pH conditions, efficiently degrading CIP even in the presence of complex matrices such as Cl−, NO3−, SO42−, NH4+, or humic acid (HA) in water bodies, although HCO3− was found to inhibit CIP degradation. This study significantly enhances our understanding of the interaction between reduced sulfur sites and ROS in PAA-based advanced oxidation processes (AOPs), offering a promising technology for efficient antibiotic treatment in water purification.

Peroxymonosulfate Activation by Fe@N Co-Doped Biochar for the Degradation of Sulfamethoxazole: The Key Role of Pyrrolic N

In this study, Fe, N co-doped biochar (Fe@N co-doped BC) was synthesized by the carbonization–pyrolysis method and used as a carbocatalyst to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) removal. In the Fe@N co-doped BC/PMS system, the degradation efficiency of SMX (10.0 mg·L−1) was 90.2% within 40 min under optimal conditions. Radical quenching experiments and electron spin resonance (ESR) analysis suggested that sulfate radicals (SO4•−), hydroxyl radicals (•OH), and singlet oxygen (1O2) participated in the degradation process. After the reaction, the proportion of pyrrolic N decreased from 57.9% to 27.1%. Pyrrolic N served as an active site to break the inert carbon network structure and promote the generation of reactive oxygen species (ROS). In addition, pyrrolic N showed a stronger interaction with PMS and significantly reduced the activation energy required for the reaction (∆G = 23.54 kcal/mol). The utilization potentiality of Fe@N co-doped BC was systematically evaluated in terms of its reusability and selectivity to organics. Finally, the intermediates of SMX were also detected.

Design of a hybrid nanoscaled skin photoprotector by boosting the antioxidant properties of food waste-derived lignin through molecular combination with TiO2 nanoparticles

TiO2 nanoparticles loaded with pistachio shell lignin (8 % and 29 % w/w) were prepared by a hydrothermal wet chemistry approach. The efficient interaction at the molecular level of the biomacromolecule and inorganic component was demonstrated by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–Visible (UV–Vis), Fourier transform infrared (FT-IR), dynamic light scattering (DLS), and electron paramagnetic resonance (EPR) analysis. The synergistic combination of lignin and TiO2 nanoparticles played a key role in the functional properties of the hybrid material, which exhibited boosted features compared to the separate organic and inorganic phase. In particular, the hybrid TiO2-lignin nanoparticles showed a broader UV–Vis protection range and remarkable antioxidant performance in aqueous media. They could also better protect human skin explants from the DNA damaging effect of UV radiations compared to TiO2 as indicated by lower levels of p-H2A.X, a marker of DNA damage, at 6 h from exposure. In addition, the samples could protect the skin against the structural damage occurring 24 h post UV radiations by preventing the loss of keratin 10. These results open new perspectives in the exploitation of food-waste derived phenolic polymers for the design of efficient antioxidant materials for skin photoprotection in a circular economy perspective.

Solar-activated tin oxide photocatalysis for efficient naphthenic acids removal and toxicity reduction in oil sands process water

This research studied, for the first time, the effect of activating tin oxide (SnO2) under simulated solar light for treating real oil sands process water (OSPW). The solar/SnO2 system effectively eliminated fluorophore organic contaminants, classical naphthenic acids (O2-NAs), and oxidized NAs (Oxy-NAs) from OSPW. The best experimental conditions to remove over 90 % of O2-NAs were found to be 0.5 g/L SnO2 under 8 h of irradiation. HO• and O2•– species identified by electron paramagnetic resonance (EPR) analysis played an important role in the degradation of NAs and other contaminants in real OSPW. The initial toxic effects of untreated OSPW were noticeably reduced after treatment, with a reduction of approximately 50 % in acute toxicity using Microtox® bioassay and over 80 % in the level of bioavailable hydrocarbons. In addition, the process also demonstrated a significant reduction in immunotoxicity as measured using an immune cell bioassay and reduced the toxic effects on Staphylococcus warneri using an adapted bacterial minimal inhibitory concentration (MIC) viability assay. These results suggest that treated OSPW by SnO2 under solar light has high environmental compatibility, indicating it is safe for reuse in further applications.

Enhanced Antibacterial Activity of Carbon Dots: A Hybrid Approach with Levofloxacin, Curcumin, and Tea Polyphenols

Bacterial infections and their increasing resistance to antibiotics pose a significant challenge in medical treatment. This study presents the synthesis and characterization of novel carbon dots (CDs) using levofloxacin (Lf), curcumin (Cur), and tea polyphenols (TP) through a facile hydrothermal method. The synthesized curcumin-tea polyphenol@carbon dots (Cur-TP@CDs) and levofloxacin-tea polyphenol@carbon dots (Lf-TP@CDs) were characterized using transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy, confirming their unique structural and chemical properties. Cur-TP@CDs exhibited an average particle size of 1.32 nanometers (nm), while Lf-TP@CDs averaged 1.58 nm. Both types demonstrated significant antibacterial activity, with Lf-TP@CDs showing superior effectiveness against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) in broth dilution and disc diffusion assays. Biofilm inhibition assays revealed a significant reduction in biofilm formation at higher concentrations. The ultraviolet-visible (UV-vis) and photoluminescence (PL) spectral analyses indicated efficient photon emission, and electron paramagnetic resonance (EPR) analysis showed increased singlet oxygen generation, enhancing bactericidal effects. Live and dead bacterial staining followed by scanning electron microscopy (SEM) analysis confirmed dose-dependent bacterial cell damage and morphological deformities. These findings suggest that Cur-TP@CDs and Lf-TP@CDs are promising antibacterial agents, potentially offering a novel approach to combat antibiotic-resistant bacterial infections.

Visible-light-driven Z-scheme ZnTe/WO3 heterojunction for simultaneous elimination of tetracycline and Cu(II)

Z-Scheme heterojunction photocatalysts can effectively suppress the recombination of charge carriers while maintaining high redox capacity. In this study, ZnTe/WO3 (ZW) Z-scheme heterojunction photocatalysts were synthesized using a hydrothermal method, and a series of photocatalytic materials were prepared for the simultaneous removal of tetracycline (TC) and Cu(II) from water. The physicochemical and photoelectrochemical properties of the catalytic materials were characterized through various methods, including SEM, XRD, XPS, and others. The experimental results indicate that the ZW-10 % composite material exhibits the most significant removal efficiency for pollutants. Within 150 min of visible light irradiation, the removal rates for TC and Cu(II) reach 73.8 % and 73.3 %, respectively, representing a substantial improvement compared to individual ZnTe and WO3. Free radical capture experiments and electron spin resonance analysis reveal that ·O2− and ·OH are the key reactive species responsible for TC oxidation, while electrons (e−) dominate the reduction of Cu(II).

MoS2 coupled with ball milling co-modified sludge biochar to efficiently activate peroxymonosulfate for neonicotinoids degradation: Dominant roles of SO4•-, 1O2 and surface-bound radicals

An efficient catalyst of molybdenum disulfide (MoS2) coupled with ball milling modified sludge biochar (BMSBC) was prepared to efficiently activate peroxymonosulfate (PMS) for neonicotinoids elimination. As expected, 95.1% of imidacloprid (IMI) was degraded by PMS/BMSBC system within 60 min and it was accompanied by the outstanding mineralization rate of 71.9%. The superior pore structures, rich defects, oxygen-containing functional groups and grafted MoS2 on BMSBC offered excellent activation performance for PMS. The influencing factor experiments demonstrated that PMS/BMSBC system performed high anti-interference to wide pH range and background constituents (e.g., inorganic ions and humic acid). Quenching experiments and electron paramagnetic resonance analysis revealed that SO4•−, 1O2, and surface-bound radicals played critical roles in IMI degradation. Electron donors on biochar activated PMS , producing surface radicals. The lone pair electrons within the Lewis basic site of C=O on BMSBC enhanced PMS decomposition by facilitating the cleavage of the -O-O- bond in PMS to release 1O2. The activation process of PMS by MoS2 accelerated the oxidation of Mo (IV) to Mo (VI) to generate SO4•−. Based on the transformed products (TPs), four degradation pathways of IMI in PMS/BMSBC system were suggested, and all TPs toxicity levels were lower than that of IMI by ECOSAR analysis. Additionally, BMSBC exhibited outstanding sustainable catalytic activity towards PMS activation with the well accepted degradation rate of 71.3% for IMI even after five reuse cycles. PMS/BMSBC system also exhibited satisfactory degradation rates (>71.8%) for IMI in various real waters (e.g., sewage effluent, and livestock wastewater). Furthermore, PMS/BMSBC system also offered a favorable broad-spectrum elimination performance for other typical neonicotinoids (e.g., thiamethoxam, clothianidin, thiacloprid) with the degradation rates over 98%. This study has developed a desirable neonicotinoids purification technology in view of its high degradation/mineralization rate, outstanding detoxification performance, satisfied anti-interference to ambient conditions and sustainable sludge management.

Modulating long-lived ultrafast charge carrier recombination in type-I MoS2/CdS photocatalyst achieving optimal H2 evolution

Maximizing charge carrier efficiency is crucial for enhancing photocatalyst systems’ capacity to achieve outstanding photocatalytic hydrogen evolution (PHE). Herein, an I-type CdS nanorod/MoS2 nanoflowers heterojunction was successfully fabricated and kinetic transportof charge carriers was being investigated with electron paramagnetic resonance (EPR) analysis, surface photovoltage (SPV), femtosecond transient absorption (fs-TA) measurements and related density functional theory (DFT) calculations, etc. The in-situ dynamic study conducted using fs-TA reveals that the optimal CdS/MoS2 ratio (3CM), when excited by a 380 nm pump, exhibits a quasi-discrete exciton hot carrier cooling time of 0.35 picoseconds (ps), with interfacial electron transfer occurring in approximately 21.90 ps. In this context, MoS2 enhances the efficiency of interfacial electron transfer by passivating surface shallow trapped states, which were observed to be only 8.62 ps in pure CdS. Moreover, the kinetic coupling of long-lived charge separation (approximately 4440 ps) within the 3CM heterojunction, across various ratios of CdS/MoS2, is identified as a key factor in enhancing visible-light-driven PHE. This enhancement achieves remarkable rates of up to 31.094 mmol h-1 g-1, surpassing the performance of physically mixed CdS-MoS2 without chemical bonding by an impressive factor of 31. Our findings highlight the importance of tailored cocatalyst ratios in modulating the charge recombination for enhanced photocatalytic activity.

Iron nanoparticles enhance the efficiency of single-atom Fenton-like catalyst by boosting Fe-NX activity

Single-atom catalysts (SACs) have been widely employed for the removal of organic contaminants via advanced oxidation processes (AOPs). The underlying principle involves central metal atoms that interact synergistically with surrounding atoms in specific ensembles to adsorb reactants and facilitate catalytic reactions. However, comprehensive studies exploring the ensemble effect of SACs in combination with metal nanoparticles relatively rare. In this study, we have synthesized a highly active iron single-atom catalyst (Fe@BC), which features both Fe-Nx coordination sites and iron nanoparticles. Fe@BC exhibits remarkable adsorption and degradation capabilities for bisphenol A across a wide pH range from 3.0 to 11.0. Scavenging experiments coupled with electron paramagnetic resonance analysis have revealed that •OH and O2•− are the key reactive oxygen species within the Fe@BC/PAA system, with •OH playing a crucial role in the removal of bisphenol A (BPA). Our comprehensive characterization analysis has validated the simultaneous presence of Fe nanoparticles and Fe-Nx sites, which are crucial for the catalyst's high activity. Furthermore, our experimental data highlight the importance of the synergistic effect between these two components. Density Functional Theory calculations have provided additional insights, showing that the presence of iron nanoparticles significantly boosts the Fe-Nx sites' activity. This enhancement is achieved by increasing adsorption energy, promoting electron transfer to peracetic acid (PAA), and decreasing the energy barrier for the formation of active species. These findings are vital for the strategic refinement of Fe single-atom catalysts for PAA-based advanced oxidation processes.

New insights into the singlet oxygen-independent formation of TEMPO signals in electron paramagnetic resonance analysis

Electron paramagnetic resonance (EPR) is currently the most commonly used technique for measurement of singlet oxygen (1O2) in advanced oxidation processes. However, the characteristic EPR signal associated with 1O2 (2,2,6,6-tetramethylpiperidine-N-oxide radical, TEMPO) can be generated via alternative pathways not involving 1O2, leading to misinterpreted results. In this study, in-situ EPR analysis was used to re-examine the interaction between peroxymonosulfate (PMS), a common oxidant, and 2,2,6,6-tetramethyl-4-piperidinol (TEMP), the spin-trapping agent of 1O2. It was found that TEMPO could be generated in TEMP/PMS system over a broad pH range (3.0–11.0). The pathway for TEMPO formation was the direct oxidation of TEMP by PMS, and 1O2 was not involved. Furthermore, the intensity of TEMPO (ITEMPO) followed a reverse parabolic pattern as the [TEMP]/[PMS] ratios changed across all pH values. Kinetic analysis unveiled three distinct patterns (continuous linear increase; linear increase followed by a lower rate of increase; increase followed by reaching a plateau) in ITEMPO. Finally, an electron transfer mechanism was proposed for the conversion of TEMP to TEMPO by PMS. The results from this study are expected to advance the understanding of 1O2-independent formation of TEMPO in TEMP/PMS and to mitigate the interference during the detection of 1O2 by EPR.

Investigation of the efficacy of graphite-sulfur iron tailing composite catalysts for activation of peroxydisulfate for rhodamine B degradation.

Herein, a novel graphite/sulfur iron tailing composite was applied as a peroxydisulfate (PDS) activator for rhodamine B (RhB) degradation in the water. The superior catalytic efficiency of graphite/sulfur iron tailing was achieved through radical (SO4•- and •OH) and non-radical (1O2) processes according to the radical quenching experiments and electron paramagnetic resonance analysis. The carbonyl group and Fe species were the main active sites on the surface of graphite/sulfur iron tailing, which was demonstrated by combining Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and reaction kinetic experiments, and a possible degradation mechanism was also proposed. Overall, activated with 0.30g/L of C-1, PDS achieved a 94.8% removal rate for RhB and maintained a removal rate of over 85% even after five consecutive operation cycles, and this study will benefit the application of iron/carbon composite materials in practical water treatment.

Observation of magnetic dimers in the diluted triangular-lattice spin liquid candidate NaYbO2

The triangular-lattice spin liquid (QSL) candidate NaYbO2 is magnetically diluted by Lu doping, forming homogeneous solid solutions NaYb1-xLuxO2 (0≤ x<1.0). A combination of structural, magnetic, and pulsed high-field electron spin resonance analysis shows that the lattice parameters and the Curie-Weiss temperature θCW vary almost linearly with x, and the crystal electric field environment of the Yb/Lu ions persists during the Lu doping. The statistical distribution analysis of clusters and the deduced linear θCW ∼ x relation indicate that the nearest neighbor exchange J does not change with magnetic dilution. Interestingly, with the magnetization measurement at 0.39 K, we have observed Seff = 1/2 antiferromagnetic Yb-Yb dimers in NaYb0.02Lu0.98O2, which is manifested as a magnetization step at μ0Hc = 2.68 T due to the transition between singlet and triplet states. Thus, the intradimer interaction is directly determined as J/kB = −5.15 K. Surprisingly, this value is close to the interaction of undoped NaYbO2, supporting the theoretical analysis of clusters. Our study provides a method of estimating the magnetic interaction of QSL materials through magnetic dilution. The statistical distribution analysis of magnetic clusters suggests that through a small amount of Lu doping (x < 0.5), the QSL state in NaYbO2 can continue to be maintained.

An electron paramagnetic resonance time-course study of oxidative stress in the plasma of electronic cigarette exposed rats.

The long-term consequences of electronic cigarette (Ecig) use in humans are not yet known, but it is known that Ecig aerosols contain many toxic compounds of concern. We have recently shown that Ecig exposure impairs middle cerebral artery (MCA) endothelial function and that it takes 3days for MCA reactivity to return to normal. However, the sources contributing to impairment of the endothelium were not investigated. We hypothesized that the increased levels of oxidative stress markers in the blood are correlated with impaired MCA reactivity. We used electron paramagnetic resonance (EPR) spectroscopy to examine plasma from 4-month-old male Sprague-Dawley rats that were exposed to either air (n=5) or 1h Ecig exposure, after which blood samples were collected at varying times after exposure (i.e., 1-4, 24, 48 and 72h postexposure, n=4 or 5 in each time group). The EPR analyses were performed using the redox-sensitive hydroxylamine spin probe 1-hydroxy-3-carboxymethyl-2,2,5,5-tetramethyl-pyrrolidine (CMH) to measure the level of reactive oxidant species in the plasma samples. We found that EPR signal intensity from the CM• radical was significantly increased in plasma at 1-4, 24 and 48h (P<0.05, respectively) and returned to control (air) levels by 72h. When evaluating the EPR results with MCA reactivity, we found a significant negative correlation (Pearson's P=0.0027). These data indicate that impaired cerebrovascular reactivity resulting from vaping is associated with the oxidative stress level (measured by EPR from plasma) and indicate that a single 1h vaping session can negatively influence vascular health for up to 3 days after vaping. HIGHLIGHTS: What is the central question of this study? Does the time course of oxidative stress triggered by electronic cigarette exposure follow the cerebral vascular dysfunction? What is the main finding and its importance? Electron paramagnetic resonance analysis shows that the oxidative stress induced after a single 1h exposure to electronic cigarette aerosol takes ≤72h to return to normal, which mirrors the time course for vascular dysfunction in the middle cerebral artery that we have reported previously.

Constructing interfacial electric field with rich oxygen vacancy modulated heterojunction FeVO4-MgZnAl LDH for enhanced photocatalytic degradation of doxycycline

FeVO4 nanorods were synthesized and integrated with plate-like MgZnAl layered double hydroxide (LDH) using a combination of sonochemical coprecipitation and hydrothermal methods. The resulting FeVO4-MgZnAl LDH nanocomposites (FeVO4-MZA NCs) were engineered to enhance photocatalytic performance through an S-scheme charge transfer mechanism. These NCs exhibited exceptional photocatalytic activity, achieving 93.7% degradation of doxycycline (DXY) which is significantly outperforming its counterparts, FeVO4(29.8%) and MgZnAl LDH (49.8%). Detailed analysis using scavenging tests and electron spin resonance (ESR) analysis confirmed that the photoexcited charges follow the S-scheme pathway, leading to the generation of hydroxyl (•OH) and superoxide (O2•⁻) radicals. This mechanism remarkedly improves the catalytic efficiency of FeVO4-MZA NCs with a kinetic rate constant of 4 - 9 times higher than those of its individual components. The photocatalyst's were comprehensively characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (UV-vis-DRS), photoluminescence (PL) spectroscopy, and electrochemical impedance spectroscopy (EIS). The FeVO₄-MZA NCs demonstrated remarkable stability and reusability, indicating their suitability for large-scale water treatment applications. Additionally, the non-toxic nature of FeVO4-MZA NCs, coupled with effective charge carrier separation and reduced recombination rates, establishes them as highly efficient photocatalysts for the removal of pharmaceutical contaminants from aquatic systems.

Accelerated Fe3+/Fe2+ cycle in Mo2C-based Fe catalyst to promote peroxymonosulfate activation

The harmful impact of organic pollutants on aquatic ecosystems underscores the pressing need for effective remediation. While activating peroxymonosulfate (PMS) with Fe catalyst offers a promising approach for eliminating these pollutants, its widespread use is hindered by the sluggish regeneration of Fe2+ from Fe3+. Here, this study demonstrates for the first time that combining an Fe catalyst with Mo2C (Fe-Mo2C) enhances the Fe³⁺/Fe2⁺ cycle, thereby improving PMS activation. The Fe-Mo2C/PMS system achieved near-complete degradation of carbamazepine (CBZ) within only 8 minutes, with an impressive observed rate constant (kobs) of up to 0.624 min-1, about 15 times greater than that of Fe-C catalyst. It also exhibits the capability to degrade a broad range of common antibiotics, phenols, and dye-like organic compounds. Through electron paramagnetic resonance (EPR) analysis and quenching experiments, it was verified that hydroxyl radicals (·OH), sulfate radicals (SO4·-), singlet oxygen (1O2), and superoxide radicals (·O2-) species during the reaction, with the former three serving as the primary active species. These findings offer a hopeful avenue for the systematic development and enhancement of catalysts specifically designed to efficiently remediate organic pollutants in wastewater.

A highly efficient Co-based catalyst for peroxymonosulfate activation for rapid degradation of RhB over a wide pH range

Cobalt-based materials have been demonstrated to be effective heterogeneous catalysts for peroxymonosulfate activation in degrading many refractory organic pollutants. In this study, a new cobalt-based catalyst was prepared using cobalt chloride hexahydrate (CoCl2·6H2O) as the Co2+ source, 2,3-pyrazine dicarboxylic acid and 3,6-DI-4-pyridyl-1,2,4,5-tetrazine (4-PYTZ) as ligands. This catalyst was employed as a peroxymonosulfate activator for the degradation of Rhodamine B(RhB). The results indicated that the prepared Co-based catalyst can effectively degrade RhB dye in aqueous solution by activating peroxymonosulfate (PMS). Specifically, when the initial concentration of RhB was 20 mg/L, its degradation rate exceeded 98 % within merely 9 min. The factors influencing the activation of PMS by the Co-based catalyst were examined, including PMS concentration, reaction temperature, solution pH, and the concentration of organic pollutants. Stability and reusability tests demonstrated that the prepared catalyst exhibited good stability, with the degradation rate of RhB remaining above 97 % after four repetitive experiments. Free radical quenching experiments and electron paramagnetic resonance (EPR) analyses revealed that sulfate radicals (SO4−) and hydroxyl radicals (OH) are the primary reactive radicals accountable for the degradation process. Additionally, it displayed excellent adaptability over a wide pH range, particularly within the pH levels ranging from 5 to 9. This study demonstrates that the prepared Co-based catalyst can serve as a stable and effective option for degrading organic dyes in wastewater treatment applications.

Enhanced photoelectric properties of TiO2 nanorod arrays through modulation of precursor concentration

This study synthesized titanium dioxide (TiO2) nanorod arrays and investigated their morphology and defect to the photoelectric response by varying the titanium isopropoxide (TTIP) precursor concentration from 0 to 66 mM. The vertically aligned rutile TiO2 nanorods exhibited film thicknesses ranging from 1 to 4.5 μm when the TTIP concentration equaled or exceeded 33 mM. Their rod length and diameter displayed a linear increase with the TTIP concentration. TiO2 arrays synthesized with a TTIP concentration of 33 mM exhibited the highest photoelectric response, measuring 52 μA/cm2 under xenon-lamp irradiation at a bias voltage of 0.8 V (vs. the Ag/AgCl reference). Notably, photoactivity was observed in the visible-light region as well. Photoluminescence spectra indicated a substantial reduction in electron-hole recombination compared to TiO2 arrays prepared from higher TTIP concentrations. X-ray photoelectron spectroscopy and electron paramagnetic resonance analyses confirmed the presence of oxygen vacancies. Time-resolved photoluminescence spectra corroborated an extended electron lifetime, suggesting that surface oxygen vacancies facilitated the separation of photoexcited charge carriers. The presence of oxygen vacancies, combined with the unique array morphology, resulted in enhanced photocurrent density.

Periodate-driven efficient degradation of diverse pharmaceuticals with iodine-doped MnO2

This research investigated the development of a novel catalyst for contaminant remediation. The strategy involved enhancing the catalytic effectiveness of MnO2 by strategically incorporating iodine, resulting in I-MnO2. Electron paramagnetic resonance (EPR) spectroscopy confirmed an augmentation in oxygen vacancies upon iodine inclusion, leading to increased catalytic activity. I-MnO2 was evaluated as an efficient catalyst within an advanced oxidation process for ciprofloxacin removal through periodate activation. The system achieved a 91.2 % degradation of 20 ppm ciprofloxacin within 9 min, demonstrating a strong correlation between catalyst and oxidant dosages. The I-MnO2/IO4¯ system exhibited remarkable stability across a broad pH range and minimal susceptibility to ionic strength variations, water anions, and humic acid presence. Quenching experiments coupled with EPR analysis suggested the involvement of singlet oxygen (1O2) and iodate radicals (IO3•) generated from the interaction of the metastable Mn(IV)-O-IO3 species with ciprofloxacin. X-ray photoelectron spectroscopy analysis of Mn 2p and O 1s orbitals, performed before and after reactions, further corroborated the role of I-MnO2 in facilitating periodate activation by promoting the conversion of Mn(II) and Mn(III) to Mn(IV) species. This innovative catalyst demonstrates exceptional efficiency in eliminating high concentrations of organic pollutants, suggesting its potential for practical and cost-effective applications in wastewater treatment.

Efficient ofloxacin degradation via peroxymonosulfate activation using an S-scheme MoS2/Co3O4 heterojunction composite under visible light: Performance and mechanistic insights

Sulfate-radical-mediated photocatalysis technology peroxymonosulfate (PMS) activation via visible light irradiation shows great promise for water treatment applications. However, its effectiveness largely depends on the bifunctional performance of photocatalysis and PMS activation provided by the catalysts. In this study, we successfully synthesized a novel S-scheme MoS2/Co3O4 (MC) heterojunction composite by a hydrothermal method and employed it for the first time to activate PMS for ofloxacin (OFX) degradation under visible light irradiation. The MC-5/PMS/Vis system achieved an impressive 85.11% OFX degradation efficiency within 1 min and complete OFX removal within 15 min under optimal conditions, with an apparent first-order kinetics rate constant of 0.429 min−1. Reactive species trapping experiments and electron spin resonance analysis identified 1O2, h+, and •O2− as the primary active species responsible for OFX degradation. Photoelectrochemical analyses and density functional theory calculations indicated the formation of a built-in electric field between MoS2 and Co3O4, which enhanced the separation and migration of photoinduced carriers. Additionally, the Co–Mo interaction further increased the yield of dominant reactive species, thereby boosting photocatalytic activity. This work underscores the potential of visible-light-assisted PMS-mediated photocatalysis using Co3O4-based catalysts for effective pollutant control.