Electron Spin Resonance Technique Research Articles

A co-precipitation route for the preparation of eco-friendly Cu-Al-layered double hydroxides with efficient tetracycline degradation.

The construction of novel efficient catalysts for the treatment of organic pollutants in the aqueous environment is essential. The lamellar-like Cu-Al layered double hydroxides (CuAl-LDHs) with various mole ratios were synthesized by a simple route of co-precipitation, and the corresponding degradation characteristic was tested for the removal of tetracycline (TC) using PMS activation. The degradation efficiency of TC over CuAl-LDHs increased up to 93% within 10min for the Cu/Al mole ratio of 3:1 and almost not changed at a higher mole ratio. For further calcining the optimal catalyst at 300 ℃, the degradation efficiency of TC was found to be increased to 96%. Sulfuric radicals and singlet oxygen were analyzed to be the main reason for the change in degradation characteristics, which was proved by radical quenching experiments and electron paramagnetic resonance technique. The parameters including PMS concentration, catalyst dosage, and reaction temperature on the TC degradation as well as the degradation mechanism for PMS activation were elaborated. The best proportion of CuAl-LDHs owned splendid stability and catalytic activity after reusing, which showed enormous potential in practical application.

Effect of Ultraviolet Illumination on the Fixation of Silver Ions on Zinc Oxide Films and Their Photocatalytic Efficiency

This study focuses on the fabrication and characterization of nanostructured zinc oxide films deposited on glass substrates using sol–gel dip-coating methods. The thin films are functionalized with silver ions at various Ag+ concentrations (10−2, 10−3, 10−4 M) through room temperature ion fixation process with and without ultraviolet (UV) illumination. Physicochemical characterization techniques, such as employing Scanning Electron Microscopy with Energy-dispersive X-ray spectroscopy (SEM-EDX), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Ultraviolet–Visible Spectroscopy and Electron Paramagnetic Resonance (EPR) techniques. The SEM-EDX and XRD confirmed a characteristic ganglia-like structure with a hexagonal crystalline structure. The photocatalytic performance and available surface area of the pure and Ag films are investigated in the removal of methylene blue dye under UV and visible light illumination and in darkness. It is observed that the photocatalytic activity increases proportionally to the Ag+ ion concentration: ZnO < Ag(10−4 M)/ZnO, < Ag(10−3 M)/ZnO < Ag(10−2 M)/ZnO. Moreover, the catalysts modified under UV illumination during the fixation treatment (Ag-UV/ZnO) exhibited a higher photocatalytic efficiency and degraded the dye in comparison with those without a light source (Ag/ZnO). The experimental results are confirmed using total organic carbon (TOC) analysis. The optimal silver concentration (10−2 M) is established, which shows the highest photocatalytic efficiency (in both cases of ion fixation treatment). The results can be used as a guideline for the development of co-catalyst-functionalized semiconductor photocatalysts.

CdS Nanoparticles Supported by Cobalt@Carbon-Derived MOFs for the Improved Adsorption and Photodegradation of Ciprofloxacin.

The design and synthesis of efficient photocatalysts that promote the degradation of organic pollutants in water have attracted extensive attention in recent years. In this work, CdS nanoparticles are grown in situ on Co@C derived from metal-organic frameworks. The resulting hierarchical CdS/Co@C nanostructures are evaluated in terms of their adsorption and photocatalytic ciprofloxacin degradation efficiency under visible-light irradiation. The results show that, apart from offering a large surface area (55.69 m2·g-1), the prepared material can effectively suppress the self-agglomeration of CdS and enhance the absorption of visible light. The CdS/Co@C-7 composite containing 7% wt Co@C has the highest photodegradation rate, and its activity is approximately 4.4 times greater than that of CdS alone. Moreover, this composite exhibits remarkable stability after three successive cycles of photocatalysis. The enhanced photocatalytic performance is largely ascribed to the rapid separation of electron-hole pairs and the effective electron transfer between CdS and Co@C, which is confirmed via electrochemical experiments and photoluminescence spectra. The active substance capture experiment and the electron spin resonance technique show that h+ is the main active entity implicated in the degradation of CIP, and accordingly, a possible mechanism of CIP photocatalytic degradation over CdS/Co@C is proposed. In general, this work presents a new perspective on designing novel photocatalysts that promote the degradation of organic pollutants in water.

Visible-light-driven oxygen vacancy and carbon doping of C@TiO2-x photocatalyst for enhanced pollutants degradation performance.

Oxygen Vacancy (OVs) and carbon doping of the photocatalyst body will significantly enhance the photocatalytic efficiency. However, synchronous regulation of these two aspects is challenging. In this paper, a novel C@TiO2-x photocatalyst was designed by coupling the surface defect and doping engineering of titania, which can effectively remove rhodamine B (RhB) and has a relatively high performance with wide pH range, high photocatalytic activity and good stability. Within 90 minutes, the photocatalytic degradation rate of RhB by C@TiO2-x (94.1% at 20 mg/L) was 28 times higher than that of pure TiO2. Free radical trapping experiments and electron spin resonance techniques reveal that superoxide radicals (•O2-) and photogenerated holes (h+) play key roles in the photocatalytic degradation of RhB. This study demonstrates the possibility of regulating photocatalysts to degrade pollutants in wastewater based on an integrated strategy.

Anisotropic Multiexciton Quintet and Triplet Dynamics in Singlet Fission via Pulsed Electron Spin Resonance.

The quintet triplet-pair state may be generated upon singlet fission and is a critical intermediate that dictates the fate of excitons, which can be exploited for photovoltaics, information technologies, and biomedical imaging. In this report, we demonstrate that continuous-wave and pulsed electron spin resonance techniques such as phase-inverted echo-amplitude detected nutation (PEANUT), which have emerged as the primary tool for identifying the spin pathways in singlet fission, probe fundamentally different triplet-pair species. We directly observe that the generation rate of high-spin triplet pairs is dependent on the molecular orientation with respect to the static magnetic field. Moreover, we demonstrate that this observation can prevent incorrect analysis of continuous-wave electron spin resonance (cw-ESR) measurements and provide insight into the design of materials to target specific pathways that optimize exciton properties for specific applications.

Reactivity of tert‐butylperoxyl radical with some phenylthiazolidine derivatives and probucol

AbstractThe hybrid molecule phenylthiazolidine derivatives and probucol were kinetically examined as antioxidants (AOs) in scavenging tert‐butylperoxyl radical (t‐BuOO•) with comparable to the reference AO, butylated hydroxytoluene (BHT). The anti‐t‐BuOO• reactivity of phenylthiazolidine derivatives and probucol was established using the direct kinetic electron paramagnetic resonance (EPR) technique with pulse reactant injection. Absolute values of the bimolecular reaction rate constants and antiradical capacities of the studied compounds were measured from −63 to 0°C. The main antiperoxylradical sites of the compounds under study were revealed.High removal ability of t‐BuOO• by (2‐(4‐hydroxyphenyl)thiazolidine), 4‐[thiazolidin‐2‐yl]benzene‐1,2‐diol, 2‐(4‐hydroxyphenyl)thiazolidine‐4‐carboxylic acid and probucol was connected with the reaction of hydrogen atom abstraction from phenolic OH group.Weaker antiperoxylradical reactivity of 2‐phenylthiazolidine was connected with the slower reaction of hydrogen atom abstraction from benzylic C–H bond in reference to nitrogen and sulfur atoms compared with the phenolic OH group. It is found that sulfide groups had much weaker participation in antiperoxylradical reactivity of the studied compounds. It is concluded that removal of alkylperoxyl radicals by oxidizable phenylthiazolidine derivatives and probucol may partially account for biological activity of their compounds.

Photocatalytic depolymerization of lignin via oxidizing cleavage of Cα-Cβ bonds in micellar aqueous media

Photocatalytic depolymerization of lignin to prepare high-value chemicals is a promising way to promote the valuable utilization of lignin. However, the complexity and stubbornness of lignin structure seriously decrease the photocatalytic efficiency and selectivity. Herein, the micellar aqueous media (SDS-8/HCl) consisting of sodium lauryl sulfonate and hydrochloric acid was successfully prepared. Photocatalyst TiO2 and SDS-8/HCl system can effectively depolymerize the typical β-1 lignin models and ethanol organosolv lignin to value-added chemicals by oxidizing cleavage of lignin Cα-Cβ bonds. The addition of hydrochloric acid solution (1 mol/L) improves the selectivity of photocatalytic breaking of lignin Cα-Cβ bonds. Chlorine ions are oxidized to chlorine radicals by photogenerated holes and hydroxyl radicals, dramatically increasing the photocatalytic efficiency. Electron paramagnetic resonance technique and Gas chromatography–mass spectrometry were used to demonstrate the presence of chlorine radicals. Under optimal conditions, the conversion of substrate Dpol is 98.4 %, and the obtained products are mainly benzaldehyde and benzoic acid. Isotope labeling experiments show that water is also involved in photocatalytic reactions and the oxygen needed to form the product benzaldehyde comes from water. Single-electron transfer processes are possible photocatalytic mechanisms that differ from the previous reports. Importantly, water and chlorine ions were found to be involved in photocatalytic reactions for the first time and promote the cleavage of lignin Cα-Cβ bonds. This work provides new ideas for photocatalytic cleavage of lignin Cα-Cβ bonds in heterogeneous photocatalytic systems using micellar aqueous media.

Room Temperature Electron Spin Coherence in Photogenerated Molecular Spin Qubit Candidates.

One of the main challenges in the emerging field of molecular spintronics is the identification of new spin qubit materials for quantum information applications. In this regard, recent work has shown that photoexcited chromophore-radical systems are promising candidates to expand our repertoire of suitable candidate molecules. Here, we investigate a series of three chromophore-radical compounds composed of a perylene diimide (PDI) chromophore and a stable 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) radical by transient electron paramagnetic resonance (EPR) techniques. We explore the influence of isotope labeling of the TEMPO moiety on the EPR spectra and electron spin coherence times of the molecular quartet states generated upon photoexcitation and illustrate that (i) a coherent manipulation of the spin state is possible in these systems even at room temperature and that (ii) a spin coherence time of 0.7 μs can be achieved under these conditions. This demonstration of electron spin coherence at ambient temperatures paves the way for practical applications of such systems in functional molecular devices.

Coupling of Fe-N-C single atom catalyst and ferrocene-modified graphitic carbon nitride as an efficient photocatalyst for removal of pollutants from water

Graphitic carbon nitride (CN) is a promising photocatalyst in wastewater treatment field; however, CN suffers from sluggish photogenerated charge separation. Herein, a single atom catalyst (Fe-N-C) coupled with ferrocene-functionalized CN (CN-Fc) heterostructured composite (FCF-0.05) with superior photocatalytic activity was fabricated. Bisphenol A (BPA) can be removed completely over FCF-0.05/PMS/Vis system within 60 min, the corresponding apparent rate constant (k) was 24 times and 10 times higher than those of CN/Vis and CN/PMS/Vis systems, respectively, which was derived from the efficiently charge separation since generated interfacial heterojunction. Moreover, FCF-0.05/PMS/Vis system exhibited high stability and superior catalytic activity in real water and outdoor environment. Furthermore, the BPA degradation mechanism and pathway have been identified by combination experimental (quench testing, electron paramagnetic resonance and liquid chromatography-mass spectrometry techniques) and density functional theory (DFT) calculations method, providing insight of synthesis of cost-effective photocatalyst with outstanding catalytic activity.

A Physicochemical Study of the Antioxidant Activity of Corn Silk Extracts.

Corn silk (CS) extracts are reported to contain flavonoids (appx. 59.65 mg quercetin/g), polysaccharides (appx. 58.75 w.%), steroids (appx. 38.3 × 10-3 to 368.9 × 10-3 mg/mL), polyphenols (appx. 77.89 mg/GAE/g) and other functional biological substances. This study investigated the antioxidant activity of corn silk extracts related to their functional compounds. The radical scavenging effect of corn silk extracts was evaluated by the spin-trapping electron paramagnetic resonance (EPR) technique, 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonate) (ABTS•+) free radical measurement, ferric ion-reducing antioxidant power, and copper ion reductive capacity. It was found that the maturity stage of CS plant materials and the applied extraction procedure of their bioactive compounds have a profound effect on the radical scavenging capacity. Differences in the antioxidant activity of the studied corn silk samples based on their maturity were also confirmed. The strongest DPPH radical scavenging effect was observed for the corn silk mature stage (CS-M)stage (CS-MS) (65.20 ± 0.90)%, followed by the silky stage (CS-S) (59.33 ± 0.61)% and the milky stage (CS-M) (59.20 ± 0.92)%, respectively. In general, the final maturity stage (CS-MS) provided the most potent antioxidant effect, followed by the earliest maturity stage (CS-S) and the second maturity stage (CS-M).

Investigation of resonance-stabilized radicals associated with soot particle inception using advanced electron paramagnetic resonance techniques

In order to tackle the climate emergency, it is imperative to advance cleaner technologies to reduce pollutant emission as soot particles. However, there is still a lack of complete understanding of the mechanisms responsible for their formation. In this work, we performed an investigation devoted to the study of persistent radicals potentially involved in the formation of soot particles, by continuous wave and pulsed electron paramagnetic resonance. This work provides experimental evidence of the presence in nascent soot of highly branched, resonance-stabilized aromatic radicals bearing aliphatic groups, linked together by short carbon chains, and reinforced by non-covalent π-π interactions. These radicals appear to be highly specific of nascent soot and quickly disappear with the increasing soot maturity. Their presence in nascent soot could represent an underestimated health risk factor in addition to the already well documented effect of the high specific surface and the presence of harmful adsorbates.

Z-Scheme CdIn2S4/Bi2WO6 Heterojunction for High Piezo-Photo Synergetic Performance

The piezoelectric effect triggered by mechanical energy could establish an internal electric field to effectively modulate the separation behavior of carriers. Herein, a novel CdIn2S4/Bi2WO6 (CIS/BWO) piezo-photocatalyst for removing diclofenac (DCF) from water was constructed for the first time. Encouragingly, the photocatalytic degradation activity of CIS/BWO was effectively promoted through the piezoelectric effect. Specifically, 10% CIS/BWO exhibited promising DCF degradation performance under co-excitation of light irradiation and ultrasonic vibration, with a degradation efficiency of 99.9% within 40 min, much higher than that of pure photocatalysts (72.3%) and piezocatalysts (60.3%). Meanwhile, an in-depth study of the charge carrier separation mechanism of the CIS/BWO composite under the piezo-photo synergy condition was proposed. Both the built-in electric field induced by the piezoelectric effect in BWO and the Z-scheme transfer path of the CIS/BWO heterojunction are beneficial to interfacial charge transfer. Moreover, the Z-scheme mechanism was further demonstrated by trapping experiments and the electron spin resonance (ESR) technique. Finally, the corresponding intermediates of DCF over CIS/BWO composites and possible degradation pathways were also investigated by DFT calculations and liquid chromatography-mass spectrometry.

Implications of Protein Interaction in the Speciation of Potential VIVO-Pyridinone Drugs.

Vanadium complexes (VCs) are promising agents for the treatment, among others, of diabetes and cancer. The development of vanadium-based drugs is mainly limited by a scarce knowledge of the active species in the target organs, which is often determined by the interaction of VCs with biological macromolecules like proteins. Here, we have studied the binding of [VIVO(empp)2] (where Hempp is 1-methyl-2-ethyl-3-hydroxy-4(1H)-pyridinone), an antidiabetic and anticancer VC, with the model protein hen egg white lysozyme (HEWL) by electrospray ionization-mass spectrometry (ESI-MS), electron paramagnetic resonance (EPR), and X-ray crystallography. ESI-MS and EPR techniques reveal that, in aqueous solution, both the species [VIVO(empp)2] and [VIVO(empp)(H2O)]+, derived from the first one upon the loss of a empp(-) ligand, interact with HEWL. Crystallographic data, collected under different experimental conditions, show covalent binding of [VIVO(empp)(H2O)]+ to the side chain of Asp48, and noncovalent binding of cis-[VIVO(empp)2(H2O)], [VIVO(empp)(H2O)]+, [VIVO(empp)(H2O)2]+, and of an unusual trinuclear oxidovanadium(V) complex, [VV3O6(empp)3(H2O)], with accessible sites on the protein surface. The possibility of covalent and noncovalent binding with different strength and of interaction with various sites favor the formation of adducts with the multiple binding of vanadium moieties, allowing the transport in blood and cellular fluids of more than one metal-containing species with a possible amplification of the biological effects.

Unveiling the structure–activity relationships of ofloxacin degradation by Co3O4-activated peroxymonosulfate: From microstructures to exposed facets

As a fluoroquinolone antimicrobial agent, ofloxacin (OFX) has been widely used, consequently causing serious damage to the ecological environment. Advanced oxidation processes based on persulfate activation (SR-AOPs) are widely applied to degrade stubborn organic contaminants in wastewater treatment. Co3O4 is being extensively investigated as a promising persulfate catalyst in SR-AOPs. In this work, four Co3O4 polycrystals with specific morphologies were synthesized and used to activate peroxymonosulfate (PMS) for OFX degradation. The obtained samples and corresponding precursors were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and N2 adsorption/desorption isotherms. Experimental results showed that 30 mg·L-1 OFX could be completely removed in the lamella-like Co3O4/PMS system within 30 min under ordinary conditions. The underlying degradation mechanism was elaborated by high-resolution TEM (HRTEM) combined with density functional theory (DFT) calculations. Based on quenching experiments and the electron paramagnetic resonance (EPR) technique, sulfate radicals were identified as the dominant reactive oxygen species (ROS) in the lamella-like Co3O4/PMS system, and superoxide radicals, hydroxyl radicals, and singlet oxygen made minor contributions to the degradation of OFX. Possible degradation pathways were proposed based on DFT calculations and Fukui theory and confirmed by ultrahigh-performance liquid chromatography-quadrupole-time of flight mass spectrometry (UHPLC-QTOF/MS). Furthermore, quantitative structure–activity relationship (QSAR) prediction was used to evaluate the developmental toxicity of the corresponding intermediates.

Fluvial response to Quaternary hydroclimate in eastern Africa: Evidence from Gona, Afar, Ethiopia

The Busidima Formation in the Afar region, Ethiopia, spans the Quaternary and records the cultural evolution of the genus Homo. Yet, the Middle Pleistocene to Holocene fluvial environments in which early humans lived are undersampled in eastern Africa. This paper examines the stratigraphy, geochronology and paleoenvironments of the newly designated Odele Member of the uppermost Busidima Formation (<152 thousand years ago (ka)), which has received little attention despite representing a critical period in the evolution of early Homo sapiens and its migration out of Africa. The Odele Member is 40–50 m thick and is dated using tephrochronology, radiometric, luminescence, and electron spin resonance techniques. The member spans 151 to 7 ka, defined at the base by the widespread Waidedo Vitric Tuff (WAVT, 151 ± 16 ka modeled age and 95.4% credible interval - C.I.). There are two prominent erosional unconformities in the Odele Member, a lower one after the WAVT deposition with a modeled 95.4% C.I. range of 124–97 ka; and an upper one involving widespread alluvial fan incision commencing between 21.7 and 12.9 ka. The uppermost Odele Member also contains black, organic-rich mats, redox features, reed casts, and freshwater gastropods marking wetter conditions during the terminal Pleistocene and Early Holocene. A black, fine-grained relict soil coeval with the Halalalee paleosol bounds the top of the Odele Member and has mollic and vertic properties, weathering since ∼12 ka. These incision events and prominent paleosol development near/at the top of the Busidima Formation document Middle to Late Pleistocene Awash River incision to its present-day course. Paleo-rainfall estimates suggest that the Early Holocene-age Halalalee paleosol weathered under a climate with mean annual rainfall 10–15% higher than today. A compilation of radiocarbon ages from aquatic gastropods, carbonized wood and charcoal from the upper Odele Member shows wetter and possibly more vegetated conditions during late marine isotope stage (MIS) 3 and the African Humid Period (AHP) that are tightly coupled with precession-driven summer insolation maxima. These key findings suggest that periods of incision, aggregation, and landscape stability in the Odele Member have an orbital precession pacing. The Odele Member revises upward the age of the Busidima Formation to 7 ka, showing that it spans into the Holocene and now includes Middle and Later Stone Age archaeological traditions.

Direct Measurement and Imaging of Redox Status with Electron Paramagnetic Resonance.

Significance: Fundamental to the application of tissue redox status to human health is the quantification and localization of tissue redox abnormalities and oxidative stress and their correlation with the severity and local extent of disease to inform therapy. The centrality of the low-molecular-weight thiol, glutathione, in physiological redox balance has long been appreciated, but direct measurement of tissue thiol status in vivo has not been possible hitherto. Recent advances in instrumentation and molecular probes suggest the feasibility of real-time redox assessment in humans. Recent Advances: Recent studies have demonstrated the feasibility of using low-frequency electron paramagnetic resonance (EPR) techniques for quantitative imaging of redox status in mammalian tissues in vivo. Rapid-scan (RS) EPR spectroscopy and imaging, new disulfide-dinitroxide spin probes, and novel analytic techniques have led to significant advances in direct, quantitative imaging of thiol redox status. Critical Issues: While novel RS EPR imaging coupled with first-generation molecular probes has demonstrated the feasibility of imaging thiol redox status in vivo, further technical advancements are desirable and ongoing. These include developing spin probes that are tailored for specific tissues with response kinetics tuned to the physiological environment. Equally critical are RS instrumentation with higher signal-to-noise ratio and minimal signal distortion, as well as optimized imaging protocols for image acquisition with sparsity adapted to image information content. Future Directions: Quantitative images of tissue glutathione promise to enable acquisition of a general image of mammalian and potentially human tissue health.

Atomic and Electronic Reconstruction in Defective 0D Molybdenum Carbide Heterostructure for Regulating Lower‐Frequency Microwaves

Abstract0D nanomaterials with high efficiency of atom utilization possess extraordinary tunability over bulk materials. Precise reconstruction of atoms in a 0D nanoparticle toward tuning of crystalline phases and defects is highly desirable but remains a grand challenge. In this study, a crystallization rate‐controlled strategy is reported to achieve controllable reconstruction of atoms in situ, which inducts a series of monodisperse 0D molybdenum carbide nanoparticles (MoxC NP) that anchor on a carbon matrix with adjustable crystalline phases and atom vacancies. Aberration‐corrected transmission electron microscopy, electron paramagnetic resonance technique, density functional theory calculation, and electron holography jointly reveal the atomic reconstruction process and confirm its remarkable effects of optimizing the local electronic states and enhancing the heterointerface interactions. As a result, the optimized MoC/Mo2C heterostructure on the carbon matrix is shown to enable the promoted dielectric response and generate more than 90% absorption of lower‐frequency microwaves (the current 5th‐generation communication band). The control of atomic reconstruction may provide an effective pathway for unlocking tunable dielectric properties of 0D nanomaterials toward various technological applications.

Spin–Orbit Interaction in ZnO/MgxZn1 –xO Heterojunctions Probed by Electron Spin Resonance Spectroscopy

The spin–orbit interaction in a series of ZnO/MgxZn1 – xO heterojunctions containing a two-dimensional electron system with a wurtzite structure has been studied in detail. The spin–orbit coupling constants have been determined from the analysis of the modification of the single-particle g-factor caused by the spin–orbit interaction in the quantum Hall effect regime. The g-factor has been measured with high accuracy by the electron paramagnetic resonance technique in wide ranges of magnetic fields and electromagnetic frequencies. The spin–orbit coupling constants have been determined for a series of samples with different Mg concentrations, which has allowed us to obtain the dependence of the spin–orbit coupling constant on the two-dimensional electron density n. The measured spin–orbit coupling constant is in the range of 0.5–0.8 meV Å and quite weakly depends on n. The coefficients specifying the linear and cubic contributions to the spin–orbit interaction determined from the approximation of the experimental data are α0 = 0.48 meV Å and γ = 0.12 eV Å3, respectively. These values are correlated with results obtained by other research groups.

Singlet Oxygen Generation via an Electrochemical Reduction Method Assisted by a Ruthenium(II) Complex.

In this work, singlet oxygen (1O2) is unprecedently recorded in the electrochemical reduction of tris(2,2'-bipyridine)ruthenium(II) [Ru(bpy)32+] in an acetonitrile solution with dissolved oxygen, which is well characterized by the specific probe of Singlet Oxygen Sensor Greens and the technique of electron-spin resonance in this work. Importantly, this new electrochemical method to produce 1O2 shows higher efficiency than the conventional photodriven method. Furthermore, taken together with the inherent advantages of electrochemical techniques compared with the photochemical/chemical-driven method, this electrochemical method would inevitably show great promise in reactive-oxygen-species-related studies in the future.

One-step conversion of chemical excess sludge into functional catalyst to activate peroxymonosulfate for sulfamethoxazole degradation: Performance and mechanisms

The safe disposal of excess sludge generated from chemical wastewater treatment processes has attracted worldwide concern because of its high yield and toxicity. In our work, purified terephthalic acid excess sludge-derived biochar (PTABC) was prepared via one-step pyrolysis without additives. The prepared catalyst was demonstrated to degrade sulfamethoxazole (SMX) via the activation of peroxymonosulfate (PMS). The inhibitory effects of anions were negligible. The reactive oxygen species were investigated based on the radical scavenging experiments and electron paramagnetic resonance technique. Additionally, the electron transfer process was investigated via electrochemical measurements. The results show that the non-radical pathways take a leading role in the degradation of SMX and the corresponding contributions of sulfate radical (SO4•–), hydroxyl radical (•OH) and non-radical pathways in PTABC-700/PMS system for SMX degradation were 12.59%, 3.28%, and 84.13%, respectively. Active sites of PTABC-700 responsible for SMX degradation were also proposed. Overall, this study provides a promising strategy for converting excess sludge into functional catalysts and achieving treatment of SMX-contaminated wastewater.