Peroxymonosulfate Activation Research Articles

Strong evidence for interface-field-induced photocarrier separation in new AgFeO2-BiVO4 heterostructures and their efficient photo-Fenton degradation of ciprofoxacin

Deep elucidation of photocarrier transfer and separation mechanism is scientifically significant for developing new photocatalysts in pollutant elimination. In this study, we have immobilized AgFeO2 (AFO) nanoparticles on the surface of BiVO4 (BVO) nanobricks to construct new BVO-AFO heterostructured photocatalysts. Multiple advanced characterization techniques combined with theoretical calculations corroborate substantial evidence for the formation of built-in electric field at the BVO-AFO heterojunction interface and efficient photocarrier transfer/separation behavior and mechanism. Simulated-sunlight-driven photodegradation of ciprofoxacin (CIP) demonstrates an important enhanced photocatalysis of the heterostructure photocatalysts; particularly, the BVO-15 %AFO exhibits a photodegradation performance with η(30 min) = 89.9 % and kapp = 0.06659 min−1, which is enhanced by 4.2 (or 3.4) times over that of bare BVO (or AFO). The heterostructure-enhanced photocatalysis is benefited from the interface-field-facilitated transfer and separation of photocarriers, thus extending their lifetime and making them more probable to participate in the photocatalytic reactions. Furthermore, the BVO-AFO heterostructured photocatalysts demonstrate an important activation of peroxymonosulfate (PMS) or H2O2 to generate additional •OH and •SO4− reactive species, thus further promoting the CIP degradation. This work provides an important scientific basis for designing excellent heterostructured photocatalysts.

Nitrogen-Doped Carbon Materials for Persulfate Activation via Electron Transfer Pathways.

The incorporation of nitrogen into carbon materials is a strategy that effectively boosts their catalytic potency. Herein, a nitrogen-enriched carbon substance, designated as CN0.6, was synthesized from melamine, serving as a precursor. This substance has been established to act as an efficient catalyst devoid of metals for the activation of peroxymonosulfate (PMS). At a temperature of 25 °C, a concentration of 0.05 g/L CN0.6 along with 1 mM PMS suffices to achieve the complete degradation of concentrated tetracycline hydrochloride (TC) in a short period of 4 min. This enhanced catalytic performance is attributed to the optimal level of nitrogen doping, which elevates the pyrrolic nitrogen content and introduces additional defects characterized by an ID/IG ratio of 1.02. These factors collectively augment the adsorptive capacity for PMS and create a greater number of active sites to facilitate its activation. The dominance of a nonradical electron transfer mechanism in the CN0.6/PMS system has been confirmed through a series of analyses, including radical identification, quenching tests, and electrochemical assessments. Employing high-resolution liquid chromatography coupled with tandem mass spectrometry (LC-MS), the investigation identified three potential degradation routes for TC. Furthermore, the intermediates produced are determined to possess reduced toxicity in comparison to TC. The findings of this study offer a approach to the synthesis of highly efficient nitrogen-doped, metal-free catalysts, presenting a promising strategy for the degradation of environmental pollutants.

PTFE composite membrane with peroxymonosulfate activation self-cleaning for highly-efficient oil-water emulsion separation and dye degradation

Combining membrane separation with advanced oxidation technology can make the membrane self-cleaning, extending its service life. However, the preparation of composite membranes with excellent catalytic ability, self-cleaning performance, and stability remains a key research direction. In this study, a PTFE composite membrane with peroxymonosulfate activation self-cleaning ability was successfully prepared by in-situ growth of CoOOH and ZIF-67 on the surface of a l-DOPA/PEI modified PTFE membrane. The as-prepared membrane is superhydrophilic and has significant superoleophobic surfaces underwater, the separation efficiency of the as-prepared membrane for multiple oil-water emulsions exceeded 98.4 %. Meanwhile, the effective degradation of several organic dyes under visible light was simulated, with still high degradation efficiency (>99 %) after 10 cycles. Overall, this study puts forward a approach towards self-cleaning membranes based on PTFE material; the resulting composite membrane's high separation efficiency, stability under repeated use conditions as well as its self-cleaning ability position it as an attractive candidate for long-term wastewater purification applications.

Mechanistic insights into ultrafast degradation of electron-rich emerging pollutants by waste cyanobacteria resource utilization

Biochar has the issues with inadequate stability and low catalytic activity. In this study, two-step ball milling method was applied to synthesis carbon nitride co-modified cyanobacteria biochar (CN-BC). The optimized CN-BC can effectively activate peroxymonosulfate (PMS) to degrade emerging pollutants. The degradation rate constant of enrofloxacin in the CN-BC/PMS system reached 0.506 min−1, and 95 % of enrofloxacin could be effectively degraded within 10 min. Free radical quenching experiments and electrochemical experiments confirmed that the electron transfer and 1O2 were the main pathways in the CN-BC/PMS system. The CN-BC/PMS system has selective degradation of electron-rich pollutants, and the pollutants containing electron-donating groups are more easily degraded than those containing electron-withdrawing group. The selective degradation pathway of pollutants by CN-BC was further analyzed using density functional theory (DFT). Continuous flow CN-BC/PMS membrane system showed long-term abatement of emerging pollutants. This study improves the understanding of the mechanism of PMS activation by cyanobacterial biochar catalysts and provides a new pathway for membrane-based domain-limited catalysis.

Important role of cellulose and lignin in controlling the crystal structure of iron-carbon composite: Fe3C surpassing Fe0 in activating peroxymonosulfate

The mechanism of producing iron-carbon composites with different crystal structures by varied wood-based biomass remains unclear. Herein, cellulose and lignin as the important components of wood-based biomass were used to investigate the influence on the crystal structure of iron-carbon composites. Results showed that Fe3C could only be produced in cellulose-containing pyrolysis processes, while the pyrolysis of lignin could reduce the iron salt to Fe0. Additionally, prolonging pyrolysis time and increasing the ratio of cellulose to Fe also favored the production of Fe3C. When applied to activate peroxymonosulfate (PMS), the Fe@Cel0.5-4 typically dominated by Fe3C showed better performance than Fe@Ln1.0-4 which was dominated by Fe0 in the aspects of adsorption, electron transfer, retaining the iron species, sustainability, adaptability to complex water conditions, and the catalytic capability to degrade diclofenac (DCF). Quenching experiments and electron spin resonance results indicated the presence of free radicals (OH, SO4−, SO5− and O2−) and non-radical (1O2 and electron transfer process) pathways in both processes. However, the degradation of DCF in Fe@Cel0.5-4/PMS process was mainly dominated by 1O2 and electron transfer while was contributed by radical and nonradical pathways almost equally in Fe@Ln1.0-4/PMS process. This study may cast some light on the development of iron-carbon composites using wood-based biomass as the carbon source to synthesize the highly efficient catalyst for PMS activation.

Efficient generation of 1O2 by activating peroxymonosulfate on graphitic carbon nanoribbons for water remediation

Few-layer graphitic carbon nanoribbons (GCN) with rich defective sites were prepared by pyrolysis at 800 oC in N2 of in situ-chelated Fe-polyaniline complexes synthesized via one-pot homogeneous Fenton-like oxidative polymerization of an acidic aniline solution. A minimal amount of iron (0.47 wt%) made a pivotal role in the nanoribbon growth and graphitization of GCN, and deposited highly dispersed iron species on GCN without post-synthesis acid leaching, which greatly simplified the synthesis procedure of GCN with improved yield. GCN exhibited high activity and stability for catalytic degradation of organic pollutants with peroxymonosulfate (PMS) mainly via non-radical pathways. The influences of various operating parameters on the catalytic performance of GCN were investigated. Scavenging tests, spin-trapping electron paramagnetic resonance spectra, electrochemical analyses, and theoretical calculations unveiled that 1O2 was the main reactive oxygen species generated from synergistic activation of PMS on GCN while GCN-mediated electron transfer made a minor contribution to organic degradation.

A novel persulfate activation strategy by double Z-scheme Bi2O3/CuBi2O4/BiOBr heterojunction: Non-radical dominated pathway for levofloxacin degradation

Persulfate advanced oxidation technology (PS-AOPs) is known as a novel wastewater treatment method. Considering the poor self-stability of Bi2O3/CuBi2O4, we synthesized Bi2O3/CuBi2O4/BiOBr ternary composite material and established the non-radical pathway-dominated peroxymonosulfate (PMS) activation system. The study indicated that BiOBr promoted electron migration on the material surface. Bi2O3/CuBi2O4/BiOBr/Vis/PMS system exhibited excellent catalytic performance (86.83 % within 100 min), significantly higher than Bi2O3/CuBi2O4 (63.19 %) and BiOBr (60.35 %). Furthermore, it has strong catalytic activity and adaptability to various environmental conditions. By quenching experiments and EPR analysis, O2−∙ and 1O2 were the main active species. Finally, possible degradation pathways and intermediates were predicted through liquid mass spectrometer (LC-MS), and toxicity analysis was conducted on levofloxacin (Lev) and intermediates. The degradation mechanism may be attributed to the construction of double Z-scheme heterojunction, photogenerated electron transfer and ROS generation through the redox cycle of Cu2+/Cu+ and Bi5+/Bi3+.

Enhancement of peroxymonosulfate activation through regulating electronic structure of cobalt phthalocyanine by g-C3N4 for rhodamine B degradation

The catalytic performance of cobalt-based catalysts in Fenton-like reactions is significantly influenced by the electron density of Co centers. However, precise control of the electronic structure to enhance the degradation activity remains a challenge. This paper demonstrates a method to enhance the catalytic activity of cobalt phthalocyanine (CoPc) by modulating its electronic structure via integrating with graphitic carbon nitride (g-C3N4). The electron redistribution between g-C3N4 and CoPc was observed, resulting in electron-rich Co centers. Consequently, the CoPc/g-C3N4 composites exhibit significantly enhanced peroxymonosulfate (PMS) activation capability compared to CoPc and their physical mixtures. The improved catalytic performance is due to the electron-rich Co centers, better dispersion of CoPc, and enhanced hydrophilicity. This study proposes a novel strategy for the design of efficient PMS activation catalysts.

The preparation technology and catalytic mechanism of PVDF/PVP/a-MoSx porous membrane for water flow driven piezoelectric PMS activation

Piezoelectric catalysis couples with peroxymonosulfate (PMS) activation technology can efficiently increase the yield of reactive oxygen species (ROS). Herein, a novel flexible polyvinylidene difluoride/polyvinyl pyrrolidone/amorphous molybdenum sulfide (PVDF/PVP/a-MoSx) membrane with finger-like pore structure was prepared by non-solvent induced phase separation (NIPS) method. As a result, a-MoSx nanosheets can be exposed out of the pores to provide multiple active sites. The PVDF/PVP/a-MoSx with large dipole moment can form enhanced polarization field under water flow to accelerate the charges separation and transfer, thereby promoting the breakage of the OO bond of PMS. The mechanism of piezo-photocatalytic activated PMS was confirmed by COMSOL multiphysics simulations, electrochemical experiments, contribution of active species and DFT calculations. Moreover, a self-cycling degradation reactor was proved more effective in generating piezoelectric potential and improving the degradation efficiency, supporting the practical potential of this strategy. This study provides a new platform to develop piezoelectric porous membrane for enhanced PMS activation under low density flow water energy.

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.

Anchoring cobalt dual-atom pairs on open hollow-structured carbon via a facile in-situ synthetic strategy for enhanced advanced oxidation processes

Atomically dispersed catalysts offer unprecedented opportunities for high-efficiency Fenton-like oxidation of organic pollutants in water. However, the hazardous metal leaching of atomically dispersed catalysts hinders their practical application for wastewater treatment, while the inaccessible interior active sites in carbon substrates have been commonly overlooked. Herein, we develop a straightforward approach for tightly anchoring cobalt dual-atom pairs on nitrogen-doped open hollow carbon structure (Co-NOHC) via an in-situ polyelectrolyte nanosphere-guided strategy. The unique open hollow carbon structure benefits the electron/mass transfer and maximizes the exposure of active sites. As a result, the as-synthesized Co-NOHC exhibits outstanding peroxymonosulfate activation activity and Fenton-like performance in oxidation by taking rhodamine B degradation as an example. Remarkably, the turnover frequency of the Co-NOHC is 6.5, 26.5, and 9.3 times higher than that of the Co2+, cobalt, and its oxides, respectively, and its catalytic activity also greatly outperforms the pristine zeolitic-imidazole frameworks derived Co-based atomically dispersed catalysts. More importantly, benefitted from the stable anchoring of cobalt dual atoms, the Co2+ leaching from the Co-NOHC is greatly alleviated, as low as 0.1 mg/L after the catalytic reaction, showing outstanding stability as compared to most atomically dispersed catalysts. Furthermore, the reactive active species, including SO4−, OH and O2− radicals, and electron-transfer mechanism are demonstrated to dominate the rhodamine B removal. This work offers a new consideration for promoting the development of the advanced catalysts and their potential applications in advanced oxidation process.

Preparation of iron selenide decorated 1T/2H molybdenum disulfide catalysts for peroxymonosulfate activation: Effect of phase transition

The sulfate radical-based advanced oxidation process is recognized as an effective approach for acetaminophen (ACT) degradation. Modification of MoS2 through phase engineering can contribute to enhancing peroxymonosulfate (PMS) activation performance. In this work, we decorated MoS2 with FeSe2, aiming to alter the 1T/2H phase ratio of MoS2. Experiments and calculations suggested that the incorporation of FeSe2 increases the activation pathway through the Fe(III)/Fe(II) cycle and prompts a phase transition from 2H to 1T, providing active sites and boosting charge transfer between FeSe2 and MoS2. The optimum catalyst (FeSe2@MoS2-10) showed high efficiency in PMS activation, achieving complete removal of ACT within 20 min. The pseudo-first-order rate constant (kapp) on this catalyst is 17.7 times higher than that of the MoS2/PMS system. This study provides a new direction for promoting phase transition and improving the catalytic reactivity of MoS2-based catalysts, expanding their potential applications in pharmaceutical wastewater treatment.

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

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

Synthesis of carbon dots with tailored heteroatomic structure for achieving ultrahigh effectiveness in persulfate activation

Carbon dots (CDs) are normally feature with zero-dimensional structure, excellent solubility, good biosafety, and exceptional photoelectronic properties, thus, awakening the homogeneous-like photocatalytic potency of CDs in peroxymonosulfate (PMS) activation can afford new idea for water body remediation. Herein, we presented a facile nitrogen and sulfur co-doping strategy for the development of high-performance CDs-based photocatalysts. Through the deep investigation on the structure-activity relationship, we proposed that the incorporated pyridinic N within CDs structure could serve as efficient Lewis basic sites for PMS confinement. Importantly, the co-existence of oxidized sulfur groups and specific nitrogen speciation (pyridine N and pyrrolic N) induced unique “push-pull” effect on the photogenerated carriers within the surface state of S,N co-doped CDs. The unique synergy sites and surface hydrophilic nature conferred the CDs exceptional photocatalytic effectiveness, presenting a remarkable PMS consumption ratio of 7.62 per gram of the CDs photocatalyst within just 20 min. Profited from the improved kinetics of interfacial reactions, the CDs-photocatalyzed oxidation system that consisted largely of sulfate radicals can completely degrade rhodamine B within 12.5 min, and hold great potential in long-term operation without needing to regenerate CDs catalyst.

Degradation mechanism of metronidazole using persulfate activated by boron/copper doped biochar derived from Chlorella vulgaris

Chlorella biochar modified with boron and copper (B/Cu-BC) was created and used to break down the antibiotic metronidazole (MNZ) through peroxymonosulfate (PMS) activation. The physicochemical properties of B/Cu-BC were analyzed using SEM, BET, FTIR, XRD and XPS. The results showed that the modified Chlorella biochar, which included several oxygen-containing functional groups, exhibited a rise of 7.1 times in specific surface area and a rise of 8 times in pore volume compared to the unmodified variant. Under the optimal conditions, the B/Cu-BC+PMS system removed 86.6 % of MNZ in 90 min. The reaction mechanism of the system was confirmed by Quenching and electron paramagnetic resonance (EPR) experiments. The B/Cu-BC+PMS system was accompanied by SO4•-, •OH, •O2- and 1O2, in which •O2-was the main reactive oxygen species (ROS). The intermediates in the degradation process of MNZ were investigated using HPLC-MS, and two potential degradation pathways of MNZ were suggested. Finally, the toxicology of the intermediates from the MNZ degradation process was analyzed by toxicity estimation software tool. The bioconcentration coefficients and mutagenicity coefficients showed a significant decrease, indicating that the system could efficiently degrade the antibiotic MNZ in an environmentally friendly manner.

The preparation and characterization of WS2 nanomaterials with different morphologies and the mechanistic study of peroxymonosulfate activation for phenol degradation

Transitional metal chalcogenides like WS2 play a significant role as cocatalysts in activating PMS (peroxymonosulfate) due to their high reductivity. Three WS2 samples with different morphologies, specific surface areas, and 1 T phase contents were prepared in this study. Characterizations by SEM, TEM, BET, XRD, Raman, XPS, and catalytic degradation experiments confirmed that the a-WS2 sample exhibited the richest morphology, the largest specific surface area, the highest 1 T phase content, and the best cocatalytic performance. The a-WS2/Fe(II)/PMS system efficiently degraded 20 mg/L phenol within 15 minutes and was also effective in degrading pollutants like RhB (Rhodamine B) and OFX (Ofloxacin). Characterization predicted the degradation pathway of phenol and revealed 10 intermediate products. The degradation mechanism indicated that the presence of WS2 accelerated the conversion of Fe(III) to Fe(II), thereby further promoting the activation of PMS. ·SO4−, ·OH, and ·O2− were identified as the main active radicals in this system. a-WS2 exhibits characteristics such as high catalytic performance, good stability, high recyclability, and a low ion leaching rate, and it generates sulfur vacancies during use. This system shows promising prospects in the treatment of high-concentration organic wastewater.

Insights into performance and mechanism of CuCo2O4/MXene composite as an efficient peroxymonosulfate activator for p-nitrophenol degradation

The slow redox cycle during oxidation and the toxicity risk due to leaching of metal ions greatly hinder the practical application of transition metal-based catalysts in advanced oxidation processes. In this study, a novel layered-structured CuCo2O4/MXene composite was prepared by self-assembling CuCo2O4 spinel with two-dimensional MXene and used as a heterogeneous catalyst based on peroxymonosulfate (PMS) activation for the oxidative degradation of p-nitrophenol (4-NP). Benefiting from its unique structure, the degradation efficiency of 4-NP by CuCo2O4/MXene-activated PMS was close to 100 % within 10 min at the initial pH 7.0. Quenching experiments and electron paramagnetic resonance demonstrated that both radical (SO4•- and •OH) and non-radical (1O2) pathways were involved in the degradation of 4-NP. X-ray photoelectron spectroscopy analysis showed that the introduction of MXene could significantly promote the efficient redox cycling of Cu2+/Cu+ and Co3+/Co2+ on the catalyst surface, thus providing a continuous driving force for the PMS activation. More importantly, CuCo2O4/MXene exhibited good ionic interference resistance, high stability and low metal ion leaching rate, suggesting its potential practical application. This work not only demonstrates that CuCo2O4/MXene is a promising catalyst for the degradation of organic pollutants by PMS activation, but also provides a new idea for the development of efficient PMS-activated catalysts for pollutant degradation.

Peroxymonosulfate activation by CoO@C catalyst from integrated recycling of spent lithium-ion battery: Performance and mechanism

Developing low-cost, highly active transition metal-based catalysts for peroxymonosulfate (PMS) activation is essential but remains challenging. Herein, we proposed a novel “waste-to-energy” strategy to derive an effective PMS activator (CoO@C) by integrally utilizing the abundant Co content in the cathodes and the defective structure of anode graphite from spent lithium-ion batteries (LIBs). The CoO@C/PMS system could completely degrade atrazine (ATZ) within 15 min, along with a robust resilience to coexisting substrate and a wide pH range of 5.0–11.0. Through quenching experiments and electron paramagnetic resonance (EPR), •OH was identified as the primary reactive oxygen species (ROS) responsible for ATZ degradation. Furthermore, electron transfer between the catalyst and PMS was examined via density functional theory (DFT) calculations to elucidate the activation mechanism. The Fukui index pinpointed the vulnerable sites of ATZ, offering insights into the possible degradation pathways along with UHPLC-MS analysis. Furthermore, CoO@C was fixed on a polyethersulfone (PES) membrane for continuous degradation of ATZ, which maintained a degradation efficiency exceeding 90 % after treating 6 L of wastewater. This research provided valuable insights into the preparation of metal-based catalysts for advanced oxidation processes and achieved the sustainable utilization of spent LIBs.

Enhanced Fenton-like process on Co9S8 catalyst with Mixed-Valence Cobalt(0)/Cobalt(Ⅱ)

Peroxymonosulfate (PMS)-based Fenton-like reactions have great potential to revolutionize wastewater treatment, but achieving highly efficient decontamination at low chemical input remains extremely challenging. In this study, a carbon carrier-supported Co9S8 catalyst with Mixed-Valence Cobalt(0)/Cobalt(Ⅱ) was prepared, which enables 70.72 % PMS decomposition-rate and complete, highly efficient tetracycline (TC) removal. Through the cyclic conversion pathways of polyvalent cobalt and the auto-decomposition of PMS, which produced SO4•-, 1O2, •OH, and high-valence metals, the material’s efficiency in degrading TC through PMS activation was effectively enhanced (99.92 %). S2-, as one of the active sites, not only promotes the participation of Co3+/Co2+/Co0 in the generation of reactive oxygen species but also significantly facilitates electron transfer to further increase the catalytic reaction rate. Through metal-chelating agents, it is illustrated that Co2+ directly activates PMS to produce reactive oxygen species (ROS), while Co3+ promotes cycling. The normalized kinetic constant of Co9S8/Co-C (105.6 min−1M−1) was even four times larger than that of Co9S8 (26.4 min−1M−1). Co9S8/Co-C exhibited rapid degradation over a wide pH range and extensive cycling experiments, demonstrating its versatility and stability in various environments. Possible degradation pathways were speculated using liquid chromatography-mass spectrometry (LC-MS). Toxicological evaluations and mung bean germination toxicity tests indicated that the Co9S8/Co-C+PMS system effectively reduced toxicity. It enables the complete degradation of TC while remarkably reducing the toxic intermediates, ensuring that the catalyst is suitable for wastewater treatment applications.

Potential application of SDSO-layered double hydroxide in wastewater treatment: Synergy between hydrophobicity and activation activity

The hydrophobic surface properties of catalysts, generally overlooked in the field of sulfate radical-based advanced oxidation processes (SR-AOPs), have significant potential in enhancing the applicability of catalysts in realistic wastewater treatment. The conflicting nature of hydrophobicity and activation activity presents considerable challenges in developing heterogeneous oxidation. To overcome such limitation, herein, different surfactants were employed to regulate the surface properties of CoCu-layered double hydroxides (LDH) for the activation of peroxymonosulfate (PMS). Our results demonstrated that by comparison with sodium dodecyl sulfate (SDS) and sodium laurate (SLA), sodium dodecyl sulfonate (SDSO) regulated LDH (SDSO-LDH) exhibited the most effective interpolation of organic anions into the interlayer space, simultaneously showing efficient ability for PMS activation and hydrophobicity. The SDSO-LDH/PMS system exhibited excellent degradation performance of various emerging contaminants (ECs), with Co(IV) = O and SO4•- species identified as the dominant oxidative intermediates. Density functional theory (DFT) calculations further confirmed the thermodynamic feasibility of these reactions. Moreover, the effective degradation of intrinsic organic substances in realistic wastewater and sustained hydrophobicity establishes SDSO-LDH a competitive candidate catalyst for SR-AOPs. The synergy between activation activity and hydrophobicity offers a novel perspective for the application of SR-AOPs in wastewater treatment.