Revisiting the Iron(II)/Cobalt(II)-Based Homogenous Fenton-like Processes from the Standpoint of Diverse Metal-Oxygen Complexes.

The aqueous FeIV-oxo complex and FeIII-peroxy complex (e.g., ligand-assisted or interfacial FeIII-hydroperoxo intermediates) have been recognized as crucial reactive intermediates for decontamination in iron-based Fenton-like processes. Intermediates with terminal oxo ligands can undergo the oxygen atom exchange process with water molecules, whereas peroxides are unable to induce such exchanges. Therefore, these distinct metal-oxygen complexes can be distinguished based on the above feature. In this study, we identified previously unknown intermediates with a peroxy moiety and cobalt center that were generated during peroxymonosulfate (PMS) activation via aqueous CoII ions under acidic conditions. Results of theoretical calculations and tip-enhanced Raman spectroscopy revealed that the CoII ion tended to coordinate with the PMS anion to form a bidentate complex with a tetrahedral structure. These reactive cobalt intermediates were collectively named the CoII-PMS* complex. Depending on the inherent characteristics of the target contaminants, the CoII-PMS* complex can directly oxidize organic compounds or trigger PMS disproportionation to release hydroxyl radicals and sulfate radicals for collaborative decontamination. This work provides a comparative study between iron- and cobalt-based Fenton-like processes and proposes novel insights from the standpoint of diverse metal-oxygen complexes.

Enhancing Fenton-like reaction mediating performance of covalent organic frameworks through porosity modification.

Covalent organic framework (COF) catalytic photocatalysts mediating Fenton-like reactions have been applied to the treatment of organic dyes in printing and dyeing wastewater. However, the photocatalytic performance of original COF is often unsatisfactory. This study investigated the impact of porosity modification strategies on the performance of COF photocatalysts in mediating the removal of organic dyes via Fenton-like reaction. Porosity modification was achieved by increasing the concentration of acetic acid (HAc) catalyst during COF preparation. The modified TAPB-DMTA COF (12M COF) exhibited excellent adsorption and photocatalytic properties. The Fenton-like reaction mediated by 12M COF photocatalysis removed nearly 96% of malachite green (MG) within 20 min, with a rate constant of 0.091 min-1, which was 2.9 and 6.5 times higher than that of g-C3N4 and original COF under the same reaction conditions, respectively. Additionally, the modulation mechanism of porosity modification on COF photocatalysis was explored. The conduction band (CB) of COF was reduced from -0.14 eV to -0.38 eV after porosity modification, facilitating the generation of longer-lived O2•- in the reaction system, which was conducive to efficient MG removal. Anti-interference experiments showed that the photocatalytic Fenton-like reaction system based on 12 M COF was less affected by common anions, cations and dissolved organics, while maintaining a high MG removal rate in tap water, mid-water, secondary clarifier effluent and river water. In summary, porosity modification was an effective strategy to improve the catalytic performance of original COFs. This study presented an efficient metal-free photocatalyst modification strategy for the Fenton-like reaction while avoiding the production of toxic by-products during dye degradation.

Glucose oxidase and MnO2 functionalized liposome for catalytic radiosensitization enhanced synergistic breast cancer therapy.

In recent years, the integration of radiotherapy and nanocatalytic medicine has gained widespread attention in the treatment of breast cancer. Herein, the glucose oxidase (GOx) and MnO2 nanoparticles co-modified multifunctional liposome of GOx-MnO2@Lip was constructed for enhanced radiotherapy. Introduction of GOx would not only elevate the glucose consumption to starve the cancer cells, but also increased the endogenous H2O2 level. Meanwhile, high intracellular GSH concentration facilitated the release of Mn2+ to amplify the cytotoxic ·OH through cascade catalytic reactions within the tumor microenvironment, resulting in a favorable tumor suppression rate of 74.45 %. Furthermore, the blood biochemical and blood routine demonstrated that GOx-MnO2@Lip had no obvious toxic side effects. Therefore, this work provided a potential vehicle for synergistic cancer starving therapy, chemodynamic therapy and radiotherapy for improving therapeutic efficacy of breast cancer.

Remarkable Active Site Utilization in Edge-Hosted-N Doped Carbocatalysts for Fenton-Like Reaction.

Improving the utilization of active sites in carbon catalysts is significant for various catalytic reactions, but still challenging, mainly due to the lack of strategies for controllable introduction of active dopants. Herein, a novel "Ar plasma etching-NH3 annealing" strategy is developed to regulate the position of active N sites, while maintaining the same nitrogen species and contents. Theoretical and experimental results reveal that the edge-hosted-N doped carbon nanotubes (E-N-CNT), with only 0.29 at.% N content, show great affinity to peroxymonosulfate (PMS), and exhibit excellent Fenton-like activity by generating singlet oxygen (1O2), which can reach as high as 410 times higher than the pristine CNT. The remarkable utilization of edge-hosted nitrogen atom is further verified by the edge-hosted-N enriched carbocatalyst, which shows superior capability for 4-chlorophenol degradation with a turnover frequency (TOF) value as high as 3.82 min-1, and the impressive TOF value can even surpass those of single-atom catalysts. This work proposes a controllable position regulation of active sites to improve atom utilization, which provides a new insight into the design of excellent Fenton-like catalysts with remarkable atom utilization efficiency.

Trimetallic-doped carbon nitride achieves chondroitin sulfate degradation via a free radical degradation strategy.

Traditional Fenton principles for degrading polysaccharides, including chondroitin sulfate (CS), are fraught with limitations, such as strict pH-dependence, higher temperature requirements, desulfurization, and environmentally perilous. In this study, an effective Fenton-like system comprising trimetallic-doped carbon nitride material (tri-CN) with hydrogen-bonded melamine-cyanuric acid (MCA) supramolecular aggregates as its basic skeleton was engineered to overcome the challenges of traditional methods. Detailed material characterizations revealed that, compared to monometallic-doped or bimetallic-doped counterparts, tri-CN offered a larger surface area, higher porosity, and increased metal loading, thereby enhancing reactant accessibility and polysaccharide degradation efficiency. The characterization and activity assessment of the degraded polysaccharide revealed structurally intact products without significant desulfurization, indicating the effectiveness of the designed approach. Moreover, the degraded chondroitin sulfate CS3 catalyzed by tri-CN, exhibited promising antioxidant activity and anti-CRISPR potential. The results elucidated that the high-valent iron species in the material served as primary active sites, catalyzing the cleavage of hydrogen peroxide to generate hydroxyl radicals that subsequently attacked CS chains, leading to their fragmentation. Hence, the designed material can be efficiently applied to polysaccharide degradation, but not limited to photocatalysis, electrocatalysis, sensor, energy storage materials, and wastewater treatment.

Key role of Phyllanthus emblica L. fruit extract promotes ZVI/H2O2 process: rich titratable acid, suitable chelating ability, and antioxidant capacity.

Phyllanthus emblica L. fruit extract (PFE) was introduced to improve ZVI/H2O2 technology, and the efficiency and mechanism of PFE promoting ZVI/H2O2 technology were explored. With the introduction of PFE, the Norfloxacin (NOR) removal rate and kobs of the process were improved by 41.17% and 5.08 times, respectively. In the ZVI/H2O2/PFE process, the degradation of NOR by the attack of ROS is the main pathway for decontamination and is dominated by the heterogeneous reaction on the catalyst surface. PFE contains 13.92 g/L titratable acid and has good complexing ability and antioxidant ability. The mechanism of PFE promoting ZVI/H2O2 technology was based on lowering the pH, complemented by chelation and antioxidant capacity. With the introduction of PFE, the utilization rate of the reagent was significantly increased (7.56 times for ZVI and 3.21 times for H2O2), the applicable pH range was widened (6-9) and the iron sludge was reduced (32.80%). Meanwhile, the concept of UPR is proposed for the first time. The result is the key role to the selection of green promoters in the ZVI/H2O2 process depends on the abundance of titratable acid, followed by a certain chelating ability and antioxidant capacity.

Artificial Bacteriophages for Treating Oral Infectious Disease via Localized Bacterial Capture and Enhanced Catalytic Sterilization.

With the rapid emergence of antibiotic-resistant pathogens, nanomaterial-assisted catalytic sterilization has been well developed to combat pathogenic bacteria by elevating the level of reactive oxygen species including hydroxyl radical (·OH). Although promising, the ultra-short lifetime and limited diffusion distance of ·OH severely limit their practical antibacterial usage. Herein, the rational design and preparation of novel virus-like copper silicate hollow spheres (CSHSs) are reported, as well as their applications as robust artificial bacteriophages for localized bacterial capture and enhanced catalytic sterilization in the treatment of oral infectious diseases. During the whole process of capture and killing, CSHSs can efficiently capture bacteria via shortening the distance between bacteria and CSHSs, produce massive ·OH around bacteria, and further iinducing the admirable effect of bacterial inhibition. By using mucosal infection and periodontitis as typical oral infectious diseases, it is easily found that the bacterial populations around lesions in animals after antibacterial treatment fall sharply, as well as the well-developed nanosystem can decrease the inflammatory reaction and promote the hard or soft tissue repair. Together, the high Fenton-like catalytic activity, strong bacterial affinity, excellent antibacterial activity, and overall safety of the nanoplatform promise its great therapeutic potential for further catalytic bacterial disinfection.

Persulfate activation by biochar and iron: Effect of chloride on formation of reactive species and transformation of N,N-diethyl-m-toluamide (DEET).

Fenton-like processes using persulfate for oxidative water treatment and contaminant removal can be enhanced by the addition of redox-active biochar, which accelerates the reduction of Fe(III) to Fe(II) and increases the yield of reactive species that react with organic contaminants. However, available data on the formation of non-radical or radical species in the biochar/Fe(III)/persulfate system are inconsistent, which limits the evaluation of treatment efficiency and applicability in different water matrices. Based on competition kinetics calculations, we employed different scavengers and probe compounds to systematically evaluate the effect of chloride in presence of organic matter on the formation of major reactive species in the biochar/Fe(III)/persulfate system for the transformation of the model compound N,N­diethyl-m-toluamide (DEET) at pH 2.5. We show that the transformation of methyl phenyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO2) cannot serve as a reliable indicator for Fe(IV), as previously suggested, because sulfate radicals also induce PMSO2 formation. Although the formation of Fe(IV) cannot be completely excluded, sulfate radicals were identified as the major reactive species in the biochar/Fe(III)/persulfate system in pure water. In the presence of dissolved organic matter, low chloride concentrations (0.1 mM) shifted the major reactive species likely to hydroxyl radicals. Higher chloride concentrations (1 mM), as present in a mining-impacted acidic surface water, resulted in the formation of another reactive species, possibly Cl2•-, and efficient DEET degradation. To tailor the application of this oxidation process, the water matrix must be considered as a decisive factor for reactive species formation and contaminant removal.

Integration of single-atom photothermal catalysts with surface-localized high temperature in peroxymonosulfate-based Fenton-like systems for enhanced antibiotics degradation.

This study delves into integrating single-atom catalysts with photothermal effect in peroxymonosulfate (PMS)-based Fenton-like systems for enhanced pollutant degradation. A single-atom photothermal catalyst (Co/PMCNs) was designed using mesoporous carbon spheres as both a single-atom support and a photothermal material. Near-infrared (NIR) light was employed due to its superior thermal effect and penetration capacity in water. It was found that Co/PMCNs could generate surface-localized high temperatures for accelerating PMS activation and reducing energy gap of activation reactions, leading to improved degradation performance. Surface-localized high temperatures were demonstrated as key in distinguishing photothermal heating from external heat sources for PMS activation. Moreover, this system performed well across various operating conditions and water matrices, with Co/PMCNs showing promising recyclability. This study highlights the impact of surface-localized high temperatures on heterogeneous catalysis under NIR irradiation, and underscores the potential of integrating single-atom catalysts with photothermal effects into advanced oxidation processes for effective water pollution control.

Synergistic ROS Generation via Core-Shell Nanostructures with Increased Lattice Microstrain Combined with Single-Atom Catalysis for Enhanced Tumor Suppression.

This study emphasizes the innovative application of FePt and Cu core-shell nanostructures with increased lattice microstrain, coupled with Au single-atom catalysis, in significantly enhancing •OH generation for catalytic tumor therapy. The combination of core-shell with increased lattice microstrain and single-atom structures introduces an unexpected boost in hydroxyl radical (•OH) production, representing a pivotal advancement in strategies for enhancing reactive oxygen species. The creation of a core-shell structure, FePt@Cu, showcases a synergistic effect in •OH generation that surpasses the combined effects of FePt and Cu individually. Incorporating atomic Au with FePt@Cu/Au further enhances •OH production. Both FePt@Cu and FePt@Cu/Au structures boost the O2 → H2O2 → •OH reaction pathway and catalyze Fenton-like reactions. This enhancement is underpinned by DFT theoretical calculations revealing a reduced O2 adsorption energy and energy barrier, facilitated by lattice mismatch and the unique catalytic activity of single-atom Au. Notably, the FePt@Cu/Au structure demonstrates remarkable efficacy in tumor suppression and exhibits biodegradable properties, allowing for rapid excretion from the body. This dual attribute underscores its potential as a highly effective and safe cancer therapeutic agent.

Exudate Unidirectional Pump to Promote Glucose Catabolism Triggering Fenton-Like Reaction for Chronic Diabetic Wounds Therapy.

The massive accumulation of exudate containing high concentrations of glucose causes wound infection and triggers the release of inflammatory factors, which in turn delays the closure of diabetic wounds. In this study, a Janus membrane is constructed by combining glucose oxidase (GOx) and copper ions (Cu2+) for the treatment of diabetic wounds, which is named as Janus@GOx/Cu2+. It consists of hydrophobic, transitional, and superhydrophilic layers in a three-layer structure with gradient hydrophilicity for self-pumping properties. The Janus@GOx/Cu2+ membrane triggers a series of cascading reactions while pumping out diabetic wound exudates. First, glucose oxidase loaded onto the hydrophilic layer of the Janus@GOx/Cu2+ membrane decomposes glucose into hydrogen peroxide (H2O2) and glucuronic acid, reducing the local glucose level. The generated glucuronic acid neutralizes the local alkaline environment of chronic wounds. Simultaneously, the H2O2 interacts with the Cu2+ contained in the hydrophobic layers of the Janus@GOx/Cu2+ membrane via a Fenton-like reaction, generating hydroxyl radicals with excellent bactericidal properties. Cu2+ promotes angiogenesis and wound healing in diabetic wounds. Under the action of multiple responses, the Janus@GOx/Cu2+ membrane promotes wound healing in diabetic infections.

Enhanced Fenton Degradation of Tetracycline over Cerium-Doped MIL88-A/g-C3N4: Catalytic Performance and Mechanism.

Since enormous amounts of antibiotics are consumed daily by millions of patients all over the world, tons of pharmaceutical residuals reach aquatic bodies. Accordingly, our study adopted the Fenton catalytic degradation approach to conquer such detrimental pollutants. (Ce0.33Fe) MIL-88A was fabricated by the hydrothermal method; then, it was supported on the surface of g-C3N4 sheets using the post-synthetic approach to yield a heterogeneous Fenton-like (Ce0.33Fe) MIL-88A/10%g-C3N4 catalyst for degrading the tetracycline hydrochloride drug. The physicochemical characteristics of the catalyst were analyzed using FT-IR, SEM-EDX, XRD, BET, SEM, and XPS. The pH level, the H2O2 concentration, the reaction temperature, the catalyst dose, and the initial TC concentration were all examined as influencing factors of TC degradation efficiency. Approximately 92.44% of the TC was degraded within 100 min under optimal conditions: pH = 7, catalyst dosage = 0.01 g, H2O2 concentration = 100 mg/L, temperature = 25 °C, and TC concentration = 50 mg/L. It is noteworthy that the practical outcomes revealed how the Fenton-like process and adsorption work together. The degradation data were well-inspected by first-order and second-order models to define the reaction rate. The synergistic interaction between the (Ce0.33Fe) MIL-88A/10%g-C3N4 components produces a continuous redox cycle of two active metal species and the electron-rich source of g-C3N4. The quenching test demonstrates that •OH is the primary active species for degrading TC in the H2O2-(Ce0.33Fe) MIL-88A/10%g-C3N4 system. The GC-MS spectrum elucidates the yielded intermediates from degrading the TC molecules.

Comparison of Fenton-like catalytic activity of biochar by in-situ and ex-situ nitrogen doping: Role of carbon quantum dots.

Nitrogen-doped biochar as Fenton-like catalysts has been widely used to remove emerging pollutants in wastewater. However, the effect of in-situ and ex-situ nitrogen doping on the Fenton-like catalytic activity of biochar is unclear. In this study, the nitrogen-doped biochar was prepared by in-situ (NBC) and ex-situ (BC-N) nitrogen doping, and the Fenton-like catalytic activity of NBC and BC-N was compared for activating hydrogen peroxide (H2O2), peroxydisulfate (PDS) and peroxymonosulfate (PMS). The results showed that NBC had higher Fenton-like catalytic activity than BC-N, because the formation of carbon quantum dots (CQDs) significantly increased the adsorption capacity to H2O2, PDS and PMS. NBC could activate H2O2, PDS and PMS for degradation of sulfamethoxazole (SMX), but showed different catalytic activity and degradation mechanism. In the systems of NBC/H2O2 and NBC/PDS, CQDs played a key role in the activation of H2O2 and PDS, and surface-bound reactive species were mainly responsible for SMX degradation. In the system of NBC/PMS, NBC acted as both electron mediator and activator, direct electron transfer between PMS and SMX and surface-bound reactive species contributed to SMX degradation. This study provides an insight into the catalytic activity of NBC for H2O2, PDS and PMS.

Decolorization of RhB on three-dimensional porous CeO2/LaFeO3/SrTiO3 catalyst via photo-fenton-like catalysis.

The catalysts with three-dimensional porous (3DP) CeO2, LaFeO3 and SrTiO3 are synthesized by sol-gel method and chemical precipitation method. The resulting multi-component 3DP CeO2/LaFeO3/SrTiO3 composite material featured a high specific surface area (26.08 m2/g), which can provide more surface active sites to improve adsorption capacity and catalytic performance. The photocatalytic, Fenton-like, photo-Fenton-like performance of the catalyst are studied on decolorization of RhB under UV irradiation, respectively. 3DP CeO2/LaFeO3/SrTiO3 exhibits high catalytic performance. Compared with photocatalytic or Fenton-like performance, 3DP CeO2/LaFeO3/SrTiO3 catalyst exhibits higher photo-Fenton-like performance, facilitating efficient decolorization of the rhodamine B. Moreover, the initial reaction rate on decolorization of RhB with 3DP CeO2/LaFeO3/SrTiO3 is 10.55, 5.52, 3.67 and 1.51 times higher than that with SrTiO3, LaFeO3, 3DP CeO2 and 3DP CeO2/LaFeO3, respectively. Meanwhile, 3DP LaFeO3/CeO2/SrTiO3 has a wider pH usage range in the synergistic reaction. Finally, a catalytic mechanism for the decolorization of rhodamine B is proposed. The continuous cycling of Fe3+/Fe2+ and Ce4+/Ce3+ and the production of active substances are achieved under the photo-Fenton-like effect of the catalyst.

Superoxide radicals mediated by high-spin Fe catalysis for organic wastewater treatment.

Water resources are indispensable basic resources and important environmental carriers; the presence of organic contaminants in wastewater poses considerable risks to the health of both humans and ecosystems. Although the Fenton-like reactions using H2O2 as the oxidant to destroy organic pollutants are attractive, there are still challenges in improving reaction activity under neutral or even alkaline conditions. Herein, we designed a H2O2 activation pathway with O2•- as the main active species and elucidated that the spin interaction between Fe sites and coordinated O atoms effectively promotes the generation of the key intermediate Fe-*OOH. Furthermore, we successfully captured and analyzed the Fe-*OOH intermediate by in situ Raman spectroscopy. When applying FBOB to a continuous-flow reactor, CIP removal efficiency remained at around 90% within 600 min of continuous operation, achieving excellent efficiency, stability, and pH tolerance in removing pollutants.

Enhancing catalyst stability: Immobilization of Cu-Fe catalyst in sodium alginate matrix for methyl orange removal via Fenton-like reaction.

This study aims to enhance the stability and effectiveness of heterogeneous catalysts in Fenton-like reactions, explicitly addressing the acidity limitations inherent in traditional Fenton processes. Copper-iron was synthesized through co-precipitation, and a catalyst bead was produced from hydrogel formation. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) confirm phases in the bimetallic Copper-iron, aligning with the intended composition. Modification with alginate led to reduced metal leaching compared to the bare bimetallic counterpart, as confirmed by atomic absorption spectroscopy (AAS). Additionally, Fourier-transform infrared spectroscopy (FTIR) revealed the deactivation of alginate through the disappearance of carboxyl groups, indicating the depolymerization of the catalyst bead. Under the suggested conditions (Methyl Orange concentration of 25 mg/L, initial solution pH of 7, 2 g/L catalyst loading, concentration of hydrogen peroxide 100 mM in a 120-min reaction time), the catalyst demonstrated remarkable decolorization efficiency of Methyl Orange, achieving 97.67 %. Further highlighting its practicality, the catalyst exhibited outstanding reusability over four cycles under identical conditions, showcasing robust immobilization capabilities and sustained performance. Notably, the catalyst's magnetic properties facilitated easy separation using an external magnet. In conclusion, the developed catalyst beads offer a solution with high reusability, magnetic separability, and reduced iron leaching. The advantageous characteristics underscore its potential as a heterogeneous catalyst for wastewater treatment applications, warranting further exploration under practical conditions.

Fe/Ni bimetallic magnetic nano-alloy (INBMNA): An efficient heterogeneous catalyst for photo-Fenton-like degradation of phenol in aqueous environment.

A lot of attention has been drawn to photo-Fenton-like catalysis among advanced oxidation processes for environmental remediation applications. Herein, we have successfully fabricated iron-nickel bimetallic magnetic nano-alloy (INBMNA) as an efficient heterogeneous photo-Fenton-like catalyst using the chemical reduction method and characterized by several analytical techniques. The characterization results show that the catalyst has a spherical shape with a mesoporous nature and contains a large specific surface area. The impact of various parameters was investigated and optimized to check the catalytic performance of INBMNAs and the found results showed that excellent photo-Fenton-like activity persisted under 6.0 pH conditions for the degradation of hazardous pollutant (phenol) under solar light exposure and microwave radiation power, respectively. Additionally, the exposed INBMNA/H2O2 system provided continuous redox cycles of Fe3+/Fe2+ and Ni2+/Ni0 pair in the Fenton-active species for stable operation. The photo-Fenton-like activity was also performed to check the effect of different inorganic anions which significantly hinder phenol reduction. Besides, the steady performance of the catalyst to remove phenol was performed in tap water and river water. Free radical trapping experiments were tested to know the role of important radicals in the photo-Fenton process. Moreover, the mechanism and possible degradation pathways of phenol were checked. By cyclic degradation experiments, the performance of the catalyst is stable and almost unchanged and can be reused several times. This study provides a promising INBMNA/H2O2 system, which encourages its widespread use in environmental remediation applications.

Simultaneous enhanced antibiotic pollutants removal and sustained permeability of the membrane involving CoFe2O4/MoS2 catalyst initiated with simple H2O2 backwashing.

Membranes for wastewater treatment should ideally exhibit sustainable high permeate production, enhanced pollutant removal, and intrinsic physical rejection. In this study, CoFe2O4/MoS2 serves as a non-homogeneous phase catalyst; it is combined with polyether sulfone membranes via liquid-induced phase separation to simultaneously sustain membrane permeability and enhance antibiotic pollutant degradation. The prepared catalytic membranes have higher pure water flux (329.34 L m-2 h-1) than pristine polyethersulfone membranes (219.03 L m-2 h-1), as well as higher mean pore size, porosity, and hydrophilicity. Under a moderate transmembrane pressure (0.05 MPa), tetracycline (TC) in synthetic and real wastewater was degraded by the optimal catalytic membrane by 72.7 % and 91.2 %, respectively. Owing to the generation of the reactive oxygen species (ROS) during the Fenton-like reaction process, the catalytic membrane could exclude the natural organics during the H2O2 backwash step and selectively promote fouling degradation in the membrane channel. The irreversible fouling ratio of the catalyzed membrane was significantly reduced, and the flux recovery rate increased by up to 91.6 %. A potential catalytic mechanism and TC degradation pathways were proposed. This study offers valuable insights for designing catalytic membranes with enhanced filtration performance.

Chloride-mediated enhancement in Cu(II)-catalyzed Fenton-like reaction: The overlooked reactive chlorine species.

The practical application of Cu(II)-catalyzed Fenton-like reaction (Cu(II)/H2O2) exhibits a low efficiency in the degradation of refractory compounds of wastewater. The impact of chloride ions (Cl-) on Fenton-like reactions have been investigated, but the influence mechanism is still unclear. Herein, the presence of Cl- (5 mM) significantly accelerated the degradation of benzoic acid (BA) under neutral conditions. The degradation of BA follows pseudo-first-order kinetics, with a degradation rate 7.3 times higher than the Cu(II)/H2O2 system. Multiple evidences strongly demonstrated that this reaction enables the production of reactive chlorine species (RCS) rather than HO• and high-valent copper (Cu(III)). The kinetic model revealed that Cl- could shift reactive species from the key intermediate (Cu(III)-chloro complexes) to RCS. Dichlorine radicals (Cl2•-) was discovered to play a crucial role in BA degradation, which was largely overlooked in previous reports. Although the reaction rate of Cl2•- with BA (k = 2.0 × 106 M-1 s-1) is lower than that of other species, its concentration is 10 orders of magnitude higher than that of Cu(III) and HO•. Furthermore, the exceptional efficacy of the Cu(II)/H2O2 system in BA degradation was observed in saline aquatic environments. This work sheds light on the previously unrecognized role of the metal-chloro complexes in production the RCS and water purification.

Cu2(OH)3NO3/γ-Al2O3 catalyzes Fenton-like oxidation for the advanced treatment of effluent organic matter (EfOM) in fermentation pharmaceutical wastewater: The synergy of Cu2(OH)3NO3 and γ-Al2O3.

The secondary effluent of fermentation pharmaceutical wastewater exhibits high chromaticity, elevated salinity, and abundant refractory effluent organic matter (EfOM), presenting significant treatment challenges and environmental threats. Herein, Cu2(OH)3NO3/γ-Al2O3 was fabricated through ultrasound-assisted impregnation and calcination to catalyze the Fenton-like oxidation for degrading organic pollutants in this secondary effluent. Under neutral conditions, with 400.00 mg/L H2O2, 8 g/L catalyst, and at 30 ℃, the EfOM and CODCr removal efficiencies can reach 96.90 % and 51.56 %, respectively. The Cu2(OH)3NO3/γ-Al2O3 catalyst possesses ideal reusability, maintaining CODCr, chromaticity, and EfOM removal efficiencies at 44.44 %-64.59 %, 85.45 %-93.45 %, and 61.00 %-95.00 % over 220 h in a continuous-flow catalytic oxidation system operated at room temperatures (15-25 ℃). Electron paramagnetic resonance results and density functional theory calculations indicate that •OOH may be the predominant reactive oxygen species, facilitated by the easier elongation of the OH bond in H2O2 compared to the OO bond. The adjusted electronic structure endows Cu2(OH)3NO3/γ-Al2O3 composite sites with superior catalytic selectivity for H2O2 activation compared to Cu2(OH)3NO3 single crystal sites, with γ-Al2O3 additionally facilitating H2O2 activation through electron donation. This research highlights the efficacy of Cu2(OH)3NO3/γ-Al2O3 in the advanced treatment of complex industrial wastewater, elucidating its catalytic mechanisms and potential applications.