In situ growth of iron incorporated Ni3S2 nanosheet on nickel foam in mediating electron transfer to peroxymonosulfate for pollutant abatement.

Catalytic oxidation of organic pollutants is a well-known and effective technique for pollutant abatement. Unfortunately, this method is significantly hindered in practical applications by the low efficiency and difficult recovery of the catalysts in a powdery form. Herein, a three-dimensional (3D) framework of Fe-incorporated Ni3S2 nanosheets in-situ grown on Ni foam (Fe-Ni3S2@NF) was fabricated by a facile two-step hydrothermal process and applied to trigger peroxymonosulfate (PMS) oxidation of organic compounds in water. A homogeneous growth environment enabled the uniform and scalable growth of Fe-Ni3S2 nanosheets on the Ni foam. Fe-Ni3S2@NF possessed outstanding activity and durability in activating PMS, as it effectively facilitated electron transfer from organic pollutants to PMS. Fe-Ni3S2@NF initially supplied electrons to PMS, causing the catalyst to undergo oxidation, and subsequently accepted electrons from organic compounds, returning to its initial state. The introduction of Fe into the Ni3S2 lattice enhanced electrical conductivity, promoting mediated electron transfer between PMS and organic compounds. The 3D conductive Ni foam provided an ideal platform for the nucleation and growth of Fe-Ni3S2, accelerating pollutant abatement due to its porous structure and high conductivity. Furthermore, its monolithic nature simplified the catalyst recycling process. A continuous flow packed-bed reactor by encapsulating Fe-Ni3S2@NF catalyst achieved complete pollutant abatement with continuous operation for 240 h, highlighting its immense potential for practical environmental remediation. This study presents a facile synthesis method for creating a novel type of monolithic catalyst with high activity and durability for decontamination through Fenton-like processes.

Oxyanion-Sensitive Catalytic Activity of Ni(II)/Oxyanion Systems for Heterogeneous Organic Degradation: Differential Oxidizing Capacity of Ni(III) and Ni(IV) as High-Valent Intermediates.

This study demonstrated that NiO and Ni(OH)2 as Ni(II) catalysts exhibited significant activity for organic oxidation in the presence of various oxyanions, such as hypochlorous acid (HOCl), peroxymonosulfate (PMS), and peroxydisulfate (PDS), which markedly contrasted with Co-based counterparts exclusively activating PMS to yield sulfate radicals. The oxidizing capacity of the Ni catalyst/oxyanion varied depending on the oxyanion type. Ni catalyst/PMS (or HOCl) degraded a broad spectrum of organics, whereas PDS enabled selective phenol oxidation. This stemmed from the differential reactivity of two high-valent Ni intermediates, Ni(III) and Ni(IV). A high similarity with Ni(III)OOH in a substrate-specific reactivity indicated the role of Ni(III) as the primary oxidant of Ni-activated PDS. With the minor progress of redox reactions with radical probes and multiple spectroscopic evidence on moderate Ni(III) accumulation, the significant elimination of non-phenolic contaminants by NiOOH/PMS (or HOCl) suggested the involvement of Ni(IV) in the substrate-insensitive treatment capability of Ni catalyst/PMS (or HOCl). Since the electron-transfer oxidation of organics by high-valent Ni species involved Ni(II) regeneration, the loss of the treatment efficiency of Ni/oxyanion was marginal over multiple catalytic cycles.

Sludge-derived hydrochar modulates complete nonradical electron transfer in peroxydisulfate activation via pyrrolic-N and carbon defect: Implication for degrading electron-rich ionizable anilines compounds.

Nonradical electron transfer process (ETP) is a promising pathway for pollutant degradation in peroxydisulfate-based advanced oxidation processes (PDS-AOPs). However, there is a critical bottleneck to trigger ETP by sludge-derived hydrochar due to its negatively charged surface, inferior porosity and electrical conductivity. Herein, pyrrolic-N doped and carbon defected sludge-derived hydrochar (SDHC-N) was constructed for PDS activation to degrade anilines ionizable organic compounds (IOC) through complete nonradical ETP oxidation. Degradation of anilines IOC was not only affected by the electron-donating capacity but also proton concentration in solution because of the ionizable amino group (-NH2). Diverse effects including proton favor, insusceptible and inhibition were observed. Impressively, addition of HCO3 with strong proton binding capacity boosted aniline degradation nearly 10 times. Moreover, characterizations and theoretical calculations demonstrated that pyrrolic-N increased electron density and created positively charged surface, profoundly promoting generation of SDHC-N-S2O82-* complexes. More delocalized electrons around carbon defect could enhance electron mobility. This work guides a rational design of sludge-derived hydrochar to mediate nonradical ETP oxidation, and provides insights into the impacts of proton on anilines IOC degradation.

Enhancement of peroxymonosulfate activation with nickel foam-supported CuCo2O4 for tetracycline degradation: Performance and mechanism insights.

The modulation of bimetallic oxide structures and development of efficient, easily recoverable catalysts are expected to effectively overcome the limitations associated with powdered catalysts in activating peroxymonosulfate (PMS). In this study, CuCo2O4 was successfully immobilized on the surface of nickel foam (NF) via an electrodeposition-calcination procedure, with highly efficient activation of PMS for tetracycline (TC) degradation (0.55 min-1). Besides acting as a support carrier and providing ample active sites, NF mediated electron transport, prevented the leaching of metal ions and enhanced the efficiency of recycling. Density functional theory (DFT) calculations and experimental tests illustrated that Cu/Co dual-sites can efficiently adsorb PMS, enabling simultaneous reduction and oxidation reactions. The dual-site synergy substantially decreased the adsorption barrier and increased the electron transfer rate. Especially, the Cu+/Cu2+ redox couple acted as an electron donor and facilitated rapid charge transfer, leading to the conversion of Co3+ to Co2+. Moreover, the CuCo2O4@NF + PMS system effectively eliminated TC by employing radical pathways (SO4•-, •OH) and nonradical processes (1O2, e-). Therefore, this study introduces a new approach to overcome the limitations of powdered bimetallic oxides, providing a promising solution for practical applications.

Analyzing the active sites of carbocatalyst for peroxydisulfate activation: Specific surface area or electrochemical surface area?

Persulfates activation by various nanomaterials has been intensively reported for advanced oxidation processes (AOPs), and substantial progress has been made in understanding the mechanism. However, most of the published articles only present the unnormalized catalytic properties, which generated confusion to compare different catalysts and identify the active sites. Herein, we presented electrochemical surface area (ECSA) as a practical normalized method and confirmed the primary active sites in N-doped graphene. By controlling the aggregation state of graphene sheets to adjust the activity of doped graphite-N species, the active sites for peroxydisulfate (PDS) activation were accurately estimated. In further experiments, specific surface area (SSA, by N2-physisorption and methylene blue adsorption) and ECSA were adopted to conclude the normalized oxidation rate constant and graphitic-N was confirmed as the primary site in nitrogen-doped graphene for the carbocatalyst/PDS system. The normalized results revealed that SSA derived from inert gas on materials could not reflect the true active sites at solid-liquid interface, while ECSA considering the operated solid-liquid situation can be used for accurate estimation of the active sites. Therefore, this study suggests that ECSA integrates the properties of both kinetics and thermodynamics, which can be adopted as a useful methodology for analyzing nano-sized environmental catalysts performance.

Non-radical oxidation driven by iron-based materials without energy assistance in wastewater treatment.

Chemical oxidation is extensively utilized to mitigate the impact of organic pollutants in wastewater. The non-radical oxidation driven by iron-based materials is noted for its environmental friendliness and resistance to wastewater matrix, and it is a promising approach for practical wastewater treatment. However, the complexity of heterogeneous systems and the diversity of evolutionary pathways make the mechanisms of non-radical oxidation driven by iron-based materials elusive. This work provides a systematic review of various non-radical oxidation systems driven by iron-based materials, including singlet oxygen (1O2), reactive iron species (RFeS), and interfacial electron transfer. The unique mechanisms by which iron-based materials activate different oxidants (ozone, hydrogen peroxide, persulfate, periodate, and peracetic acid) to produce non-radical oxidation are described. The roles of active sites and the unique structures of iron-based materials in facilitating non-radical oxidation are discussed. Commonly employed identification methods in wastewater treatment are compared, such as quenching, chemical probes, spectroscopy, mass spectrometry, and electrochemical testing. According to the process of iron-based materials driving non-radical oxidation to remove organic pollutants, the driving factors at different stages are summarized. Finally, challenges and countermeasures are proposed in terms of mechanism exploration, detection methods and practical applications of non-radical oxidation driven by iron-based materials. This work provides valuable insights for understanding and developing non-radical oxidation systems.

In-Depth Investigation of Role of -BCO2 in the Degradation of Sulfamethazine by Metal-Free Biochar/Persulfate: The Mechanism of Occurrence of Nonradical Process.

The remediation of organic wastewater through advanced oxidation processes (AOPs) based on metal-free biochar/persulfate systems has been extensively researched. In this work, boron-doped alkali lignin biochar (BKC1:3) was utilized to activate peroxymonosulfate (PMS) for the removal of sulfamethazine (SMZ). The porous structure and substantial specific surface area of BKC1:3 facilitated the adsorption and thus degradation of SMZ. The XPS characterization and density functional theory (DFT) calculations demonstrated that -BCO2 was the main active site of BKC1:3, which dominated the occurrence of nonradical pathways. Neither quenching experiments nor EPR characterization revealed the generation of free radical signals. Compared with KC, BKC1:3 possessed more electron-rich regions. The narrow energy gap (ΔEgap = 1.87 eV) of BKC (-BCO2) promoted the electron transfer to the substable complex (BKC@PMS*) on SMZ, driving the electron transfer mechanism. In addition, the adsorption energy of BKC(-BCO2)@PMS was lower (-0.75 eV → -5.12 eV), implying a more spontaneous adsorption process. The O-O (PMS) bond length in BKC(-BCO2)@PMS increased significantly (1.412 Š→ 1.481 Å), which led to the easier decomposition of PMS during adsorption and facilitated the generation of 1O2. More importantly, a combination of Gaussian and LC-MS techniques was hypothesized regarding the attack sites and degradation intermediates of the active species in this system. The synergistic T.E.S.T software and toxicity tests predicted low or even no toxicity of the intermediates. Overall, this study proposed a strategy for the preparation of metal-free biochar, aiming to inspire ideas for the treatment of organic-polluted wastewater through advanced oxidation processes (AOPs).

Resolving the overlooked photochemical nitrophenol transformation mechanism induced by nonradical species under visible light.

Nitrophenols present on the surface of particulates are ubiquitous in the atmosphere. However, its atmospheric photochemical transformation pathway remains unknown, for which the crucial effect of visible light is largely overlooked, resulting in an incomplete understanding of the effects of nitrophenols in the atmospheric environment. This study delves into the photolysis mechanism of 4-nitrophenol (4NP), one of the most abundant atmospheric nitrophenol compounds, on the surface of photoactive particulates under visible light irradiation. Unexpectedly, the nonradical species (singlet oxygen, 1O2) was identified as a dominant factor in driving the visible photolysis of 4NP. The pathways of HONO and p-benzoquinone (C6H4O2) generation were clarified by acquiring direct evidence of C-N and O-H bond breakage in the nitro (-NO2) and hydroxyl (-OH) groups of 4NP. The further decomposition of HONO results in the generation of NO and hydroxyl radicals, which could directly contribute to atmospheric oxidizing capacity and complicate the PM2.5 composition. Significantly, the behavior of 1O2-induced visible photolysis of 4NP was universal on the surface of common particulates in the atmosphere, such as A1 dust and Fe2O3. This work advances the understanding of the photochemical transformation mechanism of particulate-phase atmospheric nitrophenols, which is indispensable in elucidating the role of nitrophenols in atmospheric chemistry.

Mediating peroxymonosulfate activation path in Fenton-like reaction via doping different metal atoms into g-C3N5.

Peroxymonosulfate (PMS) could be activated by either radical path or non-radical path, how to rationally mediate these two routines was an important unresolved issue. This work has introduced a simple way to address this problem via metal atom doping. It was found that Fe-doped nitrogen-rich graphitic carbon nitride (Fe-C3N5) exhibited high activity towards PMS activation for tetracycline degradation, and the degradation rate was 3.14 times higher than that of Co-doped nitrogen-rich graphitic carbon nitride (Co-C3N5). Radical trapping experiment revealed the contributions of reactive species over two catalysts were different. Electron paramagnetic resonance analysis further uncovered the non-radical activation path played a dominated role on Fe-C3N5 surface, while the radical activation path was the main routine on Co-C3N5 surface. Density functional theory calculations, X-ray photoelectron spectroscopy analysis, and electrochemical experiments provided convincing evidence to support these views. This study supplied a novel method to mediate PMS activation path via changing the doped metal atom in g-C3N5 skeleton, and it allowed us to better optimize the PMS activation efficiency.

Graphene/MoS2-assisted alum sludge electrode induces selective oxidation for organophosphorus pesticides degradation: Co-oxidation and detoxification mechanism.

Designing an electrode that can generate abundant free radicals and 1O2, which can effectively degrade and detoxify organophosphorus pesticides (OPPs) through a co-oxidation pathway, is important. In this study, we prepared a electrode GO/MoS2@AS by supporting MoS2 on alum sludge (AS) under graphene oxide (GO) nanoconfinement. The results show that the dominant role of 1O2 at the cathode and •OHads at the anode for degradation, in addition to the involvement of 1O2 in the cathodic degradation mechanism, can be attributed to the abundant precursor •O2- and H2O2. Furthermore, calculations using density functional theory and toxicity prediction of products show that the energy (∆E) requirements of •OHfree to break the C-O bond of the pyridine ring and phosphate group are higher than that required for 1O2, and this non-radical oxidation plays a key role in detoxification. In contrast, accelerating ring opening and oxidation processes are attributed to radical oxidation. Above all, the cathodic detoxification is more effective than anodic detoxification. Three prevalent OPPs, chlorpyrifos, glyphosate, and trichlorfon, were degraded in the GO/MoS2@AS system by over 90 %, with mineralization rates of 76.66 %, 85.46 %, and 82.18 %, respectively. This study provides insights into the co-oxidation degradation and detoxification mechanism mediated by 1O2 and •OHfree.

Peroxydisulfate-based Non-radical Oxidation of Rhodamine B by Fe-Mn Doped Granular Activated Carbon: Kinetics and Mechanism Study.

While numerous persulfate-based advanced oxidation processes (AOPs) have been studied based on fancy catalysts, the practical combination of Fe or Mn modified granular activated carbon (GAC) has seldom been investigated. The present study focused on a green and readily synthesized Fe-Mn bimetallic oxide doped GAC (Fe-Mn@GAC), to uncover its catalytic kinetics and mechanism when used in the peroxydisulfate (PDS)-based oxidation process for degrading Rhodamine B (RhB), a representative xenobiotic dye. The synthesized Fe-Mn@GAC was characterized by SEM-EDS, XRD, ICP-OES and XPS analyses to confirm its physicochemical properties. The catalytic kinetics of Fe-Mn@GAC+PDS system were evaluated under varying conditions, including PDS and catalyst dosages, solution pH, and the presence of anions. It was found Fe-Mn@GAC exhibited robust catalytic performance, being insensitive to a wide pH range from 3 to 11, and the presence of anions such as Cl-, SO4 2-, NO3 - and CO3 2-. The catalytic mechanism was investigated by EPR and quenching experiments. The results indicated the catalytic system processed a non-radical oxidation pathway, dominated by direct electron transfer between RhB and Fe-Mn@GAC, with singlet oxygen (1O2) playing a secondary role. The catalytic system also managed to maintain a RhB removal above 81 % in successive 10 cycles, and recover to 89.5 % after simple DI water rinse, showing great reusability. The catalytic system was further challenged by real dye-containing wastewater, achieving a decolorization rate of 84.5 %. This work not only provides fresh insight into the kinetics and mechanism of the Fe-Mn@GAC+PDS catalytic system, but also demonstrates its potential in the practical application in real dye-containing wastewater treatment.

Inhibit or promote? Trade-off effect of dissolved organic matter on the laccase-mediator system.

A biocatalytic system comprising fungal laccase and mediators can generate phenol radicals and efficiently eliminate various triarylmethane dyes. This study systematically explores the kinetic impact of dissolved organic matter (DOM), represented by humic substance (HS consisting of 90% fulvic acid, from lignite), on the decolorization of seven typical triarylmethane dyes by Trametes versicolor laccase and twenty natural mediators. Among these, 4-hydroxybenzyl alcohol (4-HA) and methyl violet (MV) undergo in-depth investigation regarding degradation products, pathways, and reaction mechanisms. In instances where HS hampers laccase-alone decolorization, such as malachite green, Coomassie brilliant blue, bromophenol blue, and acid magenta, this inhibition may persist despite mediator introduction. Conversely, in cases where HS facilitates decolorization, such as crystalline violet and ethyl violet, most laccase-mediator systems (LMSs) can still benefit. For MV decolorization by laccase and 4-HA, HS's kinetic effect is controlled by concentration and reaction time. A 5 mg/L HS increased the decolorization rate from 50% to 67% within the first hour, whereas 10 mg/L HS only achieved 45%. After 16 h of reaction, HS's impact on decolorization rate diminishes. Furthermore, the addition of HS enhances precipitation production, probably due to its involvement in polymerization with MV and mediator. Computational simulations and spectral monitoring reveal that low HS concentrations accelerate laccase-mediated demethylation by disrupting the chromophores bound to MV, thus promoting the decolorization of MV. Conversely, inhibition by high HS concentrations stems from the competitive binding of the enzyme pocket to the mediator, and the reduction of phenol free radicals in the system. Molecular docking and kinetic simulations revealed that laccase forms complexes with both the mediator and MV. Interestingly, the decolorization of MV occurred through a non-radical mechanism in the presence of HS. This work provided a reference for screening of high catalytic performance mediators to remove triarylmethane dyes in the actual water environment.

The Surface Confinement of FeO Assists in the Generation of Singlet Oxygen and High-Valent Metal-Oxo Species for Enhanced Fenton-Like Catalysis.

Transition metal compounds (TMCs) have long been potential candidate catalysts in persulfate-based advanced oxidation process (PS-AOPs) due to their Fenton-like catalyze ability for radical generation. However, the mechanism involved in TMCs-catalyzed nonradical PS-AOPs remains obscure. Herein, the growth of FeO on the Fe3O4/carbon precursor is regulated by restricted pyrolysis of MIL-88A template to activate peroxymonosulfate (PMS) for tetracycline (TC) removal. The higher FeO incorporation conferred a 2.6 times higher degradation performance than that catalyzed by Fe3O4 and also a higher interference resistance to anions or natural organic matter. Unexpectedly, the quenching experiment, probe method, and electron paramagnetic resonance quantitatively revealed that the FeO reassigned high nonradical species (1O2 and FeIV═O) generation to replace original radical system created by Fe3O4. Density functional theory calculation interpreted that PMS molecular on strongly-adsorbed (200) and (220) facets of FeO enjoyed unique polarized electronic reception for surface confinement effect, thus the retained peroxide bond energetically supported the production of 1O2 and FeIV═O. This work promotes the mechanism understanding of TMCs-induced surface-catalyzed persulfate activation and enables them better perform catalytic properties in wastewater treatment.

Oxygen Vacancy-Laden Confinement Impact on Degradation of Metal Complexes.

Oxygen vacancies (Vo) have been recognized as the superior active site for PS-mediated environmental remediation; however, the formation and activation of Vo associated with the effects of chemical and spatial environments remain ambiguous. Herein, attributing to the low defect-formation energy of Vo in the presence of sulfonate groups, an in situ nucleating Vo-laden CuO nanosheet was deliberately fabricated inside the phase of a sulfonated mesoporous polystyrene substrate (Vo-CuO@SPM). The as-prepared nanocomposite demonstrated an excellent treatment efficiency toward metal complexes [Cu-EDTA as a case] with ignorable Cu(II) leaching, and it can be repeatedly employed for 25 recycles (not limited). Mechanistically, the electron transfer and the mass transport for PDS nonradical activation were proved to be substantially enhanced by the delocalized electrons and with the assistance of the microchannel environment. This work not only establishes insight into the formation of oxygen vacancies but also reveals the PS activation mechanism in the spatially confined sites.

The inherent nature of N/P heteroatoms in Sargassum fusiforme seaweed biochar enhanced the nonradical activation of peroxymonosulfate for acetaminophen degradation in aquatic environments.

This study investigated the catalytic activity of biochar materials derived from algal biomass Sargassum fusiforme (S. fusiforme) for groundwater remediation. A facile single-step pyrolysis process was used to prepare S. fusiforme biochar (SFBCX), where x denotes pyrolysis temperatures (600 °C-900 °C). The surface characterization revealed that SFBC800 possesses intrinsic N and P heteroatoms. The optimum experimental condition for acetaminophen (AAP) degradation (>98.70%) was achieved in 60 min using 1.0 mM peroxymonosulfate (PMS), 100 mg L-1 SFBC800, and pH 5.8 (unadjusted). Moreover, the degradation rate constant (k) was evaluated by the pseudo-first-order kinetic model. The maximum degradation (>98.70%) of AAP was achieved within 60 min of oxidation. Subsequently, the k value was calculated to be 6.7 × 10-2 min-1. The scavenger tests showed that radical and nonradical processes are involved in the SFBC800/PMS system. Moreover, the formation of reactive oxygen species (ROS) in the SFBC800/PMS system was confirmed using electron spin resonance (ESR) spectroscopy. Intriguingly, both radical (O2•-, •OH, and SO4•-) and nonradical (1O2) ROS were formed in the SFBC800/PMS system. In addition, electrochemical studies were conducted to verify the electron transfer process of the nonradical mechanism in the SFBC800/PMS system. The scavenger and electron spin resonance (ESR) spectroscopy showed that singlet oxygen (1O2) is the predominant component in AAP degradation. Under optimal condition, the SFBC800/PMS system reached ∼81% mineralization of AAP within 5 min and continued to ∼85% achieved over 60 min of oxidation. Coexisting ions and different aqueous matrices were investigated to examine the feasibility of the catalyst system, and the SFBC800/PMS system was found to be effective in the remediation of AAP-contaminated groundwater, river water, and effluent water obtained from wastewater treatment plants. Moreover, the SFBC800-activated PMS system demonstrated reusability. Our findings indicate that the SFBC800 catalyst has excellent catalytic activity for AAP degradation in aquatic environments.

Size-Dependent Catalysis in Fenton-like Chemistry: From Nanoparticles to Single Atoms.

State-of-the-art Fenton-like reactions are crucial in advanced oxidation processes (AOPs) for water purification. This review explores the latest advancements in heterogeneous metal-based catalysts within AOPs, covering nanoparticles (NPs), single-atom catalysts (SACs), and ultra-small atom clusters. A distinct connection between the physical properties of these catalysts, such as size, degree of unsaturation, electronic structure, and oxidation state, and their impacts on catalytic behavior and efficacy in Fenton-like reactions. In-depth comparative analysis of metal NPs and SACs is conducted focusing on how particle size variations and metal-support interactions affect oxidation species and pathways. The review highlights the cutting-edge characterization techniques and theoretical calculations, indispensable for deciphering the complex electronic and structural characteristics of active sites in downsized metal particles. Additionally, the review underscores innovative strategies for immobilizing these catalysts onto membrane surfaces, offering a solution to the inherent challenges of powdered catalysts. Recent advances in pilot-scale or engineering applications of Fenton-like-based devices are also summarized for the first time. The paper concludes by charting new research directions, emphasizing advanced catalyst design, precise identification of reactive oxygen species, and in-depth mechanistic studies. These efforts aim to enhance the application potential of nanotechnology-based AOPs in real-world wastewater treatment.

Sn/Sb-assisted alum sludge electrodes for eliminating hydrophilic organic pollutants in self-produced H2O2 electro-Fenton system: Insights into the co-oxidation mediated by 1O2 and •OH(ads).

Few reports have focused on using particle electrodes with polar adsorbent properties in heterogeneous electro-Fenton (EF) system to improve the degradation of hydrophilic organic pollutants (HLOPs). In this study, a hydrophilic electrode Sn-Sb/AS was prepared by supporting metals Sn and Sb on alum sludge (AS), which can effectively degrade 91.68%, 92.54%, 89.62%, and 96.24% of the four types of HLOPs, chlorpyrifos (CPF), atrazine (ATZ), diuron (DIU), and glyphosate (PMG), respectively, within 40 min. The mineralization rates were 82.37%, 78.93%, 73.98%, and 85.65% for CPF, ATZ, DIU, and PMG, respectively. Based on the analysis of Electron Paramagnetic Resonance test, quenching test, and identified anthracene endoperoxide, the degradation at the cathode was attributed to non-radical oxidation via interaction with 1O2. In contrast, the anodic oxidation occurred via direct electron transfer at the anode and/or oxidation via interaction with adsorbed •OH (•OHads) around the particle electrodes. Furthermore, the reaction sites were calculated by Density functional theory (DFT) and Fukui function, corresponding to the electrophilic attack (fA-) of 1O2 and anodic direct oxidation, besides, the radical attack (fA0) of •OH(ads). Herein, this study proposes a targeted elimination strategy for HLOPs in wastewater treatment using particle electrodes with polar adsorbent properties in EF system.

Insights into mechanism of peroxymonosufate activation by Mo single-atom catalysts: Singlet oxygen evolution and role of Mo-N coordination.

Recently, the Fenton-like reaction using peroxymonosulfate (PMS) has been acknowledged as a potential method for breaking down organic pollutants. In this study, we successfully synthesized a highly efficient and stable single atom molybdenum (Mo) catalyst dispersed on nitrogen-doped carbon (Mo-NC-0.1). This catalyst was then utilized for the first time to activate PMS and degrade bisphenol A (BPA). The Mo-NC-0.1/PMS system demonstrated the ability to completely degrade BPA within just 20 min. Scavenging tests and density functional theory (DFT) calculations have demonstrated that the primary reactive oxygen species was singlet oxygen (1O2) produced by Mo-N4 sites. The self-cycling of Mo facilitated PMS activation and the transition from a free radical activation pathway to a non-radical pathway mediated by 1O2. Simultaneously, the nearby pyridinic N served as adsorption sites to immobilize BPA and PMS molecules. The exceptionally high catalytic activity of Mo-NC-0.1 derived from its unique Mo-N coordination, which markedly reduced the distance for 1O2 to migrate to the BPA molecules. The Mo-NC-0.1/PMS system effectively reduced the acute toxicity of BPA and exhibited excellent cycling stability with minimal leaching. This study presented a new catalyst with high selectivity for 1O2 generation and provided valuable insights for the application of single atom catalysts in PMS-based AOPs.

Mechanically treated Mn2O3 triggers peracetic acid activation for superior non-radical oxidation of micropollutants: Identification of reactive complexes.

This study used a simple mechanical ball milling strategy to significantly improve the ability of Mn2O3 to activate peracetic acid (PAA) for sustainable and efficient degradation of organic micropollutant (like bisphenol A, BPA). BPA was successfully removed and detoxified via PAA activation by the bm-Mn2O3 within 30 min under neutral environment, with the BPA degradation kinetic rate improved by 3.4 times. Satisfactory BPA removal efficiency can still be achieved over a wide pH range, in actual water and after reuse of bm-Mn2O3 for four cycles. The change in hydrophilicity of Mn2O3 after ball milling evidently elevated the affinity of Mn2O3 for binding to PAA, while the reduction in particle size exposed more active sites contributing partially to catalytic oxidation. Further analysis revealed that BPA oxidation in the ball mill-treated Mn2O3 (bm-Mn2O3)/PAA process mainly depends on the bm-Mn2O3-PAA complex (i.e., Mn(III)-OO(O)CCH3) mediated non-radical pathway rather than R-O• and Mn(IV). Especially, the existence of the Mn(III)-PAA complex was definitely verified by in situ Raman spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Simultaneously, density functional theory calculations determined that PAA adsorbs readily on manganese sites thereby favoring the formation of Mn(III)-OO(O)CCH3 complexes. This study advances an in-depth understanding of the underlying mechanisms involved in the manganese oxide-catalyzed activation of PAA for superior non-radical oxidation of micropollutants.

Mediated Peroxymonosulfate Activation at the Single Atom Fe-N3O1 Sites: Synergistic Degradation of Antibiotics by Two Non-Radical Pathways.

The activation of persulfates to degrade refractory organic pollutants is a hot issue in advanced oxidation right now. Here, it is reported that single-atom Fe-incorporated carbon nitride (Fe-CN-650) can effectively activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) removal. Through some characterization techniques and DFT calculation, it is proved that Fe single atoms in Fe-CN-650 exist mainly in the form of Fe-N3O1 coordination, and Fe-N3O1 exhibited better affinity for PMS than the traditional Fe-N4 structure. The degradation rate constant of SMX in the Fe-CN-650/PMS system reached 0.472 min-1, and 90.80% of SMX can still be effectively degraded within 10 min after five consecutive recovery cycles. The radical quenching experiment and electrochemical analysis confirm that the pollutants are mainly degraded by two non-radical pathways through 1O2 and Fe(IV)═O induced at the Fe-N3O1 sites. In addition, the intermediate products of SMX degradation in the Fe-CN-650/PMS system show toxicity attenuation or non-toxicity. This study offers valuable insights into the design of carbon-based single-atom catalysts and provides a potential remediation technology for the optimum activation of PMS to disintegrate organic pollutants.