Tremendously enhanced catalytic performance of Fe(III)/peroxymonosulfate process by trace Cu(II): A high-valent metals domination in organics removal.

Dissolved copper and iron ions are regarded as friendly and economic catalysts for peroxymonosulfate (PMS) activation, however, neither Cu(II) nor Fe(III) shows efficient catalytic performance because of the slow rates of Cu(II)/Cu(I) and Fe(III)/Fe(II) cycles. Innovatively, we observed a significant enhancement on the degradation of organic contaminants when Cu(II) and Fe(III) were coupled to activate PMS in borate (BA) buffer. The degradation efficiency of Rhodamine B (RhB, 20 µmol/L) reached up to 96.3% within 10 min, which was higher than the sum of individual Cu(II)- and Fe(III)- activated PMS process. Sulfate radical, hydroxyl radical and high-valent metal ions (i.e., Cu(III) and Fe(IV)) were identified as the working reactive species for RhB removal in Cu(II)/Fe(III)/PMS/BA system, while the last played a predominated role. The presence of BA dramatically facilitated the reduction of Cu(II) to Cu(I) via chelating with Cu(II) followed by Fe(III) reduction by Cu(I), resulting in enhanced PMS activation by Cu(I) and Fe(II) as well as accelerated generation of reactive species. Additionally, the strong buffering capacity of BA to stabilize the solution pH was satisfying for the pollutants degradation since a slightly alkaline environment favored the PMS activation by coupling Cu(II) and Fe(III). In a word, this work provides a brand-new insight into the outstanding PMS activation by homogeneous bimetals and an expanded application of iron-based advanced oxidation processes in alkaline conditions.

Performance enhancement and mechanism of electroenhanced peroxymonosulfate activation by single-atom Fe catalyst modified electrodes.

Peroxymonosulfate-based electrochemical advanced oxidation processes (PMS-EAOPs) have great potential for sustainable water purification, so an in-depth understanding of its catalytic mechanism is imperative to facilitate its practical application. Herein, the performance enhancement and mechanism of electroenhanced PMS activation by single-atom Fe catalyst modified carbon felt was investigated. Compared with the anode, the cathode exhibited faster bisphenol A degradation (kcathode = 0.073 vs. kanode = 0.015 min-1), increased PMS consumption (98.8 vs. 10.3%), and an order of magnitude reduction of Fe dissolution (0.068 vs. 0.787 mg L-1). Mass transfer is a key factor limiting PMS activation, while the electrostriction of water in the hydrophobic region caused by cathode electric field (CEF) significantly increased mass transfer coefficient (km, cathode = 1.49 × 10-4 vs. km, anode = 2.68 × 10-5 m s-1). The enhanced activation of PMS is a synergistic result between electroactivation and catalyst-activation, which is controlled by the applied current density. 1O2 and direct electron transfer are the main active species and activation pathway, which achieve high degradation efficiency over pH 3 to 10. Density functional theory calculations prove CEF increases the adsorption energy, lengthens the O-O bond in PMS, and promotes charge transfer. A flow-through convection unit achieves sustainable operation with high removal efficiency (99.5% to 97.5%), low electrical energy consumption (0.15 kWh log-1 m-3), and low Fe leaching (0.81% of the total single atom Fe). This work reveals the critical role of electric fields in modulating Fenton-like catalytic activity, which may advance the development of advanced oxidation processes and other electrocatalytic applications.

Impact of metal ions on PMS/Cl- disinfection efficacy: Enhancing or impeding microbial inactivation?

Peroxymonosulfate (PMS) is an eco-friendly disinfectant gaining attention. This study examined the influence of metal ions (Co(II), Cu(II), Fe(II)) on PMS disinfection with chloride ions (Cl-) against waterborne microorganisms, encompassing both bacteria and fungal spores. The findings elucidated that metal ions augment the inactivation of bacteria in the PMS/Cl- system while concurrently impeding the inactivation of fungal spores. Specifically, the PMS/Co(II)/Cl- process increased E. coli inactivation rates by 2.25 and 2.75 times compared to PMS/Co(II) and PMS/Cl-, respectively. Conversely, PMS/Me(II)/Cl- generally exhibited a diminished inactivation capacity against the three fungal spores compared to PMS/Cl-, albeit surpassing the efficacy of PMS/Me(II). For instance, the inactivation levels of A. niger by PMS/Cl-, PMS/Cu(II)/Cl-, and PMS/Cu(II) are 4.47-log, 1.92-log, and 0.11-log, respectively. Notably, fungal spores demonstrated a substantially higher resistance to disinfectants compared to bacteria. Differences in microbial susceptibility were linked to cell wall structure, composition, antioxidant defenses, and reactive species generation, such as hydroxyl radicals (•OH), sulfate radicals (SO4•-), and reactive chlorine species (RCS). This study demonstrated the novel and unique phenomenon of metal ions' dual role in modulating the PMS/Cl- disinfection process, which has not been reported before and has important implications for the field of water treatment.

Intensive investigation of the synergistic effects between electrocatalysis and peroxymonosulfate activation for efficient organic elimination.

Hybrid systems combined eletrocatalysis and Fenton-like process attract a lot of attention due their outstanding performance and unique mechanism. Here, we proposed an efficient, cost-effective, and versatile electrochemical activation (ECA) system for efficient water purification, and intensively studied the synergistic effects between electrocatalysis and peroxymonosulfate (PMS)-based advanced oxidation. The ECA system achieved complete removal of 20 ppm tetracycline hydrochloride (TCH) in 15 min, with a rate constant of 0.338 min-1. Its performance was assessed across various operational parameters (PMS dosage, pH, applied voltage, electrode interval, temperature, co-existed ions, biomass, different oxidants), demonstrating its broad applicability and stability. Excellent degradation and mineralization for other 12 kinds of refractory organic pollutants were also achieved. The outstanding performance can be attributed to the synergistic effect in the system, in which electrocatalytic reduction of dissolved oxygen generated H2O2 and O2•-, boosting the number of reactive species, such as 1O2, by interacting with PMS. Furthermore, the presence of organic matter promotes electron transfer, amplifying the system's degradation capability. These findings not only highlight the ECA system's effectiveness in organic pollutant removal but also offer insights into the underlying degradation mechanisms, paving the way for future advancements in water purification technologies.

Interlayer synergistic reaction of radical precursors for ultraefficient 1O2 generation via quinone-based covalent organic framework.

Singlet oxygen (1O2) is important in the environmental remediation field, however, its efficient production has been severely hindered by the ultrafast self-quenching of the as-generated radical precursors in the Fenton-like reactions. Herein, we elaborately designed lamellar anthraquinone-based covalent organic frameworks (DAQ-COF) with sequential localization of the active sites (C═O) at molecular levels for visible-light-assisted peroxymonosulfate (PMS) activation. Theoretical and experimental results revealed that the radical precursors (SO5·-) were formed in the nearby layers with the migration distance less than 0.34 nm, via PMS donating electrons to the photogenerated holes. This interlayer synergistic effect eventually led to ultraefficient 1O2 production (14.8 µM s-1), which is 12 times that of the highest reported catalyst. As an outcome, DAQ-COF enabled the complete degradation of bisphenol A in 5 min with PMS under natural sunlight irradiation. This interlayer synergistic concept represents an innovative and effective strategy to increase the utilization efficiency of ultrashort-lived radical precursors, providing inspirations for subtle structural construction of Fenton-like catalysts.

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

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

Activation of peroxymonosulfate by novel magnetically recyclable CoFe2O4/MXene quantum dots composites for rapid degradation of tetracycline: Synergistic performance and mechanisms.

Tetracycline (TC), a commonly used antibiotic in wastewater, poses environmental and health risks, thus demanding advanced catalysts for its effective removal. In this work, for the first time, we integrated cobalt ferrite (CoFe2O4) and MXene quantum dots (MQDs) to form magnetic heterojunctions for rapid degradation of TC in the presence of peroxymonosulfate (PMS). Anchoring MQDs on the CoFe2O4 nanoparticles remarkably promoted the overall degradation rate of TC to 98.2% within 20 min via both radical and non-radical pathways. The first-order kinetic constant was 0.170 min-1, 3.5 and 15.5 times higher than that of CoFe2O4 and MQDs alone, respectively. Quenching experiments revealed that the addition of p-benzoquinone (p-BQ) and furfuryl alcohol (FFA) reduced the degradation of TC within 20 min to 56.2% and 28.4%, respectively, indicating that the primary reactive oxygen species for TC degradation in the CoFe2O4/MQDs + PMS system are •O2- and 1O2. CoFe2O4/MQDs also exhibited superparamagnetic property, which enabled their effective recovery by external magnetic field. Their reusability was verified by retaining 81.4% of catalytic efficacy in the consecutive 8th cycle. The CoFe2O4/MQDs + PMS system also exhibited excellent practicability in natural water samples as the degradation rates in both tap water and lake water environments exceeded 90%. Three potential pathways for TC degradation were proposed based on the liquid chromatography-mass spectrometry (LC-MS) characterizations and TC progressively transformed into 13 intermediates. This work may contribute to the ongoing efforts to develop advanced catalysts and strategies for mitigating the environmental impact of antibiotic pollution, offering a pathway toward sustainable and efficient water treatment technologies.

Sustainable upcycling of copper from waste printed circuit boards with the assistance of tannic acid and Fe3+ to a magnetic heterogeneous catalyst.

The recovery and upcycling of metals from electronic waste into functional materials for wastewater treatment is a win-win strategy for simultaneously realizing electronic waste recycling and wastewater purification. This study focused on converting Cu from waste printed boards (PCBs), a common Cu-rich electronic waste, into CuFe2O4 supported on a mesoporous carbon framework (PCFT) with the assistance of Fe3+ and tannic acid (TA). Compared to the PCF prepared without TA, the resulting PCFT exhibited excellent magnetic properties, high crystallinity, lower interfacial transfer resistance, more abundant oxygen vacancies (OV), and lower metal leaching. Moreover, PCFT can serve as a superior heterogeneous catalyst to activate peroxymonosulfate to remove reactive brilliant blue KN-R from wastewater, and its catalytic activity was markedly higher than that of CFT synthesized with Cu(NO3)2·3H2O, which may be due to its higher specific surface area and more abundant OV. The combined results of scavenging experiments, electron paramagnetic resonance analysis, and electrochemical measurements implied that both radical and nonradical processes promoted the elimination of KN-R; however, •OH and SO4•- were not the major contributors. Furthermore, the PCFT exhibited high adaptability to pH and water matrices, confirming its practical application potential. These findings provide a novel strategy for the upcycling of metals from electronic waste.

Enhancing colorimetric efficiency: nanozyme-activated peroxymonosulfate for in situ 3-aminophenol detection.

A novel colorimetric approach specifically designed to effectively identify the presence of 3-aminophenol (3-AP) in environmental water is introduced. Briefly, a nitrogen-doped carbon-supported cobalt nanozyme (Co@CN-1) was synthesized and utilized to improve the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of peroxymonosulfate (PMS). Comparative catalytic reactions confirmed that the performance of PMS as an activator exceeds that of hydrogen peroxide catalytically by a factor of 3.5. The catalytic reaction parameters underwent optimization, further resulting in the derivation of a linear detection equation for 3-AP, expressed as inhibition rate (IR%) = 3.35[3-AP]-4.36 (0-20 µM, R2 = 0.994) and IR% = 1.43[3-AP] + 31.87 (20-36 µM, R2 = 0.992), with the limit of detection (LOD) of 2.84 µM. The linear relationship between 3-AP concentration and the conversion of color to grayscale value (GSV) was established by smartphones, expressed as GSV = 1.28[3-AP] + 147.10 (R2 = 0.972). Density functional theory calculations revealed that Co acts as the preferred active site for donating electrons in PMS activation. This work provides a rapid and accurate approach for monitoring 3-AP concentration, enabling real-time analysis and potentially contributing to environmental and ecological studies.

Insights into the efficient removal and mechanism of NiFeAl-LDH with abundant hydroxyl to activate peroxymonosulfate for sulfamethoxazole wastewater.

Layered double hydroxide (LDH) material with abundant OH was successfully prepared by co-precipitation method, and a water purification system of Ni2Fe0.25Al0.75-LDH activated peroxymonosulfate (PMS) was constructed to rapidly degrade sulfamethoxazole (SMX) pollutants. The optimal conditions for the degradation of SMX in the system were as follows: 0.30 g/L Ni2Fe0.25Al0.75-LDH, 0.30 mM PMS, pH = 7 and 90 % SMX was removed in 10 min and almost completely in 40 min, which was consistent with the predicted results of response surface methodology (RSM) analysis. The abundant OH in Ni2Fe0.25Al0.75-LDH could form M(O)OSO3 complexes with PMS, accelerating the generation of reactive oxygen species (ROS) and promoting the removal of SMX. Quenching experiments and electron paramagnetic resonance (EPR) spectra showed that SO4-, OH, O2- and 1O2 also existed in the system. The surface-bound SO4- and O2- contributed greatly to the removal of SMX and the electron transfer between metals was also conducive to the production of active substances. The possible degradation pathways and intermediates of SMX were proposed. The toxicity assessment software tool (T.E.S.T) and total organic carbon (TOC) results indicated that the Ni2Fe0.25Al0.75-LDH/PMS system could reduce the overall environmental risk of SMX to some extent. This study provided a new strategy for the practical application of heterogeneous catalysts in sewage treatment.

Peroxymonosulfate-assisted photocatalysis system enhanced magnetic Fe3O4@P-C3N4 treatment of tetracycline wastewater: Multi-pathways mediated electrons migration to generate reactive species.

Photocatalytic wastewater purification is essential for environmental remediation, but rapid carrier recombination and limited oxidative capacity hinder progress. This study proposes an innovative strategy by integrating homogeneous and heterogeneous electron acceptors into a g-C3N4-based photocatalytic system, significantly enhancing the multipath utilization of photogenerated electrons. A novel Fe3O4@P-C3N4 was developed to activate an advanced peroxymonosulfate-assisted photocatalysis (PAP) system, achieving complete degradation and significant mineralization of tetracycline (TC) in real water environments, outperforming others reported in the last five years. Phytic acid, as a key precursor, modifies the hollow tubular morphology and introduces phosphorus (P) heteroatoms as electronic trapping centers, enhancing the visible light response and carrier separation, thereby promoting the Fe2+/Fe3+ cycle and the formation of reactive species. Density functional theory (DFT) calculations pinpointed TC's vulnerable sites and synergically identified reactive species, revealing almost non-toxic degradation processes. Moreover, the recyclable magnetic Fe3O4@P-C3N4/PAP system demonstrates practical application potential and leaching stability in cyclic and continuous testing. This study offers unique insights into the strategic design of photocatalysts and catalytic environments, potentially advancing practical wastewater remediation.

Facile fabrication of shape-controllable and reusable nanoporous catalytic aerogels based on Co-MOF and agarose for efficient decomposition of organic pollutants in water.

Sulfate radical (SO4•-)-based advanced oxidation processes (SR-AOPs) have been studied to date by utilizing metal-organic frameworks as efficient catalysts to generate sulfate radicals by peroxymonosulfate (PMS) activation in water purification. It is important to select high-performance and reliable catalysts for efficient water remediation, and separation and recovery of catalysts are essential in the practical application of MOFs. Herein, we adapted thermally curable, shape-controllable, and cost-effective agarose (AG) as a smart matrix and ZIF-67, as a powerful catalyst to prepare nanoarchitectured aerogel (Z67@AG). This nanoporous aerogel composite can efficiently generate sulfate radicals and hydroxyl radicals by activating PMS in the nanopores. Z67@AG aerogel could be easily fabricated in various molds to make desired shapes. This approach enables its utilization for different filtering systems and demonstrates cost-effective and stable performance by mass production and reusability. In the SR-AOP, aerogel exhibited excellent catalytic decomposition performances of 95 % and 88 % efficiencies within 8 and 10 min for dye and levofloxacin, respectively. It is believed that the proposed highly catalytic nanoporous aerogel nanocomposite having cost-effectiveness, excellent catalytic activity, facile fabrication of desired shapes, and an excellent porous structure can be extended to the synthesis of various nanocomposites and emerging applications.

Functional biochar accelerates peroxymonosulfate activation for organic contaminant degradation via the specific B-C-N configuration.

Functional biochar designed with heteroatom doping facilitates the activation of peroxymonosulfate (PMS), triggering both radical and non-radical systems and thus augmenting pollutant degradation efficiency. A sequence of functional biochar, derived from hyperaccumulator (Sedum alfredii) residues, was synthesized via sequential doping with boron and nitrogen. The SABC-B@N-2 exhibited outstanding catalytic effectiveness in activating PMS to degrade the model pollutant, acid orange 7 ( =0.0655 min-1), which was 6.75 times more active than the pristine biochar and achieved notable mineralization efficiency (71.98%) at reduced PMS concentration (0.1 mM). Relative contribution evaluations, using steady-state concentrations combined with electrochemical and in situ Raman analyses, reveal that co-doping with boron and nitrogen alters the reaction pathway, transitioning from PMS activation through multiple reactive oxygen species (ROSs) to a predominantly non-radical process facilitated by electron transfer. Moreover, the previously misunderstood concept that singlet oxygen (1O2) plays a central role in the degradation of AO7 has been clarified. Correlation analysis and density functional theory calculations indicate that the distinct BCN configuration, featuring the BC2O group and pyridinic-N, is fundamental to the active site. This research substantially advances the sustainability of phytoremediation by offering a viable methodology to synthesize highly catalytic functional biochar utilizing hyperaccumulator residues.

Enhanced activation of peroxymonosulfate by ZIF-67/g-C3N4 S-scheme photocatalyst under visible light assistance for degradation of polyethylene terephthalate.

Photocatalyst-activated peroxymonosulfate (PMS) degradation of pollutants is already widely used for wastewater treatment under visible light. Polyethylene terephthalate (PET) is widely used in daily life, but waste plastics have an irreversible negative impact on the environment. In this paper, the ZIF-67/g-C3N4 S-scheme heterojunction catalyst was synthesized as a photocatalyst to achieve a good effect on PET degradation in coordination with PMS. The results indicated that PET could be degraded up to 60.63 ± 2.12 % under the combined effect of catalyst, PMS, and light. In this experiment, the influence of catalyst-to-plastic ratio, PMS concentration, aqueous pH, and inorganic anions on plastic degradation by the photocatalytic synergistic PMS system was discussed, and the excellent performance of this system for degrading PET was highlighted through a comparative test. Electron spin resonance (ESR) and free radical quenching experiments demonstrated that SO4•- contributes the largest amount to the PET degradation performance. Furthermore, results from gas chromatography and liquid chromatography-mass spectrometry (LC-MS) indicated that the plastic degradation products include CO, CH4, and organic small-molecule liquid fuels. Finally, a possible mechanism for the light/PMS system to degrade PET in water was suggested. This paper provides a feasible solution to treat waste microplastics in water.

Regulating cobalt-nitrogen function centers via Cu incorporation enhances ciprofloxacin destruction through peroxymonosulfate activation.

Metal-nitrogen (M-N) coupling has shown promise as a catalytic active component for various reactions. However, the regulation of heterogeneous catalytic materials with M-N coupling for peroxymonosulfate (PMS) activation to enhance the degradation efficiency and reusability of antibiotics remains a challenge. In this study, an efficient modulation of M-N coupling was achieved through the incorporation of Cu into Co4N to form a Cu-Co4N composite with sea urchin-like morphology assembled by numerous nano-needles using hydrothermal and nitriding processes. This modulation led to enhanced PMS activation for ciprofloxacin (CIP) degradation. The Cu-Co4N/PMS system demonstrated exceptional removal efficiency with a degradation rate of 95.85% within 30 min and can be reused for five time without obvious loss of its initial activity. Additionally, the catalyst displayed a high capacity for degrading various challenging organic pollutants, as well as remarkable stability, resistance to interferences, and adaptability to pH changes. The synergistic effect between Co and Cu facilitated multiple redox cycles, resulting in the generation of reactive oxidized species. The primary active species involved in the catalytic degradation process included 1O2, SO4•-, O2•-, •OH, and e-, with 1O2 and SO4•- playing the most significant roles. The degradation pathways and toxicity of the intermediates for CIP were unveiled. This study offers valuable insights into the regulation of M-N centers for degrading antibiotics through PMS activation.

Cobalt germanium hydroxides with asymmetric electron distribution and surface hydroxyl groups for superb catalytic degradation performances.

Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) are attractive approaches for solving the global problem of water pollution, due to the generation of highly-active reactive oxygen species (ROS). Therefore, highly-efficient PMS activation is crucial for promoting the catalytic degradation of environmental pollutants. Here, bimetallic CoGeO2(OH)2 nanosheets with abundant surface hydroxyl groups (CGH) were synthesized via a simple hydrothermal route for PMS activation and degradation of various organic contaminants for the first time. The abundant surface hydroxyl groups (≡Co-OH/≡Ge-OH) could promptly initiate PMS to generate highly-active species: singlet oxygen (1O2), sulfate radicals (SO4·-) and hydroxyl radicals (HO•), while the asymmetric electron distribution among Co-O-Ge bonds derived from the higher electronegativity of Ge than Co further enhances the quick electron transfer to promote the redox cycle of Co2+/Co3+ and Ge2+/Ge4+, thereby achieving an outstanding catalytic capability. The optimal catalyst exhibits nearly 100 % catalytic degradation performance of dyes (Methylene blue, Rhodamine B, Methyl orange, Orange II, Methyl green) and antibiotics (Norfloxacin, Bisphenol A, Tetracycline) over a wide pH range of 3-11 and under different coexisting anion conditions (Cl-, HCO3-, NO3-, HA), suggesting the excellent adaptability for practical usage. This study could potentially lead to novel perspectives on the remediation of water areas such as groundwater and deep-water areas.

Chitosan-derived N-doped carbon supported Cu/Fe co-doped MoS2 nanoparticles as peroxymonosulfate activator for efficient dyes degradation.

Peroxymonosulfate (PMS), which is dominated by free radical (SO4•-) pathway, has a good removal effect on organic pollutants in complex water matrices. In this article, a new catalyst (CFM@NC) was synthesized by hydrothermal carbonization method with chitosan (CS) as N and C precursors, and used to activate PMS to degrade dye wastewater. CFM@NC/PMS system can degrade 50 mg·L-1 rhodamine B by 99.59 % within 30 min, and the degradation rate remains as high as 97.32 % after 5 cycles. It has good complex background matrices, acid-base anti-interference ability (pH 2.6-10.1), universality and reusability. It can degrade methyl orange and methylene blue by >98 % within 30 min. The high efficiency of the composite is due to the fact that CS-modified MoS2 as a carrier exposes a large number of active sites, which not only disperses CuFe2O4 nanoparticles and improves the stability of the catalyst, but also provides abundant electron rich groups, which promotes the activation of PMS and the production of reactive oxygen species (ROS). PMS is effectively activated by catalytic sites (Cu+/Cu2+, Fe2+/Fe3+, Mo4+/Mo6+, pyridine N, pyrrole N, edge sulfur and hydroxyl group) to produce a large number of radicals to attack RhB molecules, causing chromophore cleavage, ring opening, and mineralization. Among them, free radical SO4•- is the main ROS for RhB degradation. This work is expected to provide a new idea for the design and synthesis of environmentally friendly and efficient heterogeneous catalysts.

Single-Atom Iron Catalysts with Core-Shell Structure for Peroxymonosulfate Oxidation.

The chemical tolerance of ketoenamine covalent organic frameworks (COFs) is excellent; however, the tight crystal structure and low surface area limit their applications in the field of catalysis. In this work, a porous single-atom iron catalyst (FeSAC) with a core-shell structure and high surface area was synthesized by using Schiff base COF nanospheres as the core and ketoenamine COF nanosheets growth on the surfaces. Surface defects were created using sodium cyanoborohydride etching treatment to increase specific surface area. The dye degradation experiments by peroxymonosulfate (PMS) catalyzed by the FeSAC proved that methylene blue can be degraded with a degradation rate constant of 0.125 min-1 under the conditions of 0.1 g L-1 catalyst dosage and 0.05 g L-1 peroxymonosulfate. The FeSAC/PMS system effectively degrades various pollutants in the pH range of 4-10 with over 80% efficiency for four cycles and can be recovered by soaking in iron salt solution. Free radical quenching experiments confirmed that singlet oxygen and superoxide radicals are the main active species for catalysis.

Homogeneous versus heterogeneous Mn(II) oxidation in peroxymonosulfate assisting chlorination: Synergistic role for enhanced Mn(II) oxidation in water treatment.

Removal of Mn(II) is an essential step for addressing water discoloration in water treatment utilities worldwide. However, conventional chlorination suffers from poor oxidation of Mn(II) due to its low homogeneous oxidation kinetics. This study explored the oxidation capability of a new chemical dosing strategy employing peroxymonosulfate (PMS) to assist the chlorination process (PMS@Cl2) for effective Mn(II) oxidation. The study comprehensively explored both oxidation kinetics and underlying mechanisms associated with homogeneous and heterogeneous oxidation within the PMS@Cl2 system. At an [Mn(II)]0 of 1 mg/L, chlorination demonstrated inability in oxidizing Mn(II), with <10 % oxidation even at an elevated [Cl2] of 150 µM (∼10 mg/L). By contrast, PMS completely oxidized 100 % Mn(II) within a 30-minute reaction at a much lower [PMS] of 60 µM (kobs = 0.07 min-1 and t1/2 = 9 min), demonstrating its superior Mn(II) oxidation kinetics (over one order of magnitude faster than conventional chlorine). PMS@Cl2 exhibited an interesting synergistic benefit when combining a lower dose PMS with a higher routine dose Cl2 (loPMS@hiCl2), e.g. [PMS]:[Cl2] at 15:30 or 30:30 µM. Both conditions achieved 100 % Mn(II) oxidation, with even better values of kobs and t1/2 (0.16-0.17 min-1 and ∼4 min) relative to PMS alone at 60 µM. The synergic benefit of PMS@Cl2 was attributed to distinct functions played by PMS and Cl2 in both homogeneous and heterogeneous oxidation processes. Reactive species identification excluded the possible involvement of SO4•-, OH•, or chlorine radicals in the homogeneous oxidation of the PMS@Cl2 system. Instead, the dominant species was O2•- radical generated during the reaction of Mn(II) and PMS. Furthermore, the heterogeneous oxidation emphasized the important role of combining Cl2 dosing, which demonstrated an increased reactivity and electron transfer with the Mn-O-Mn complex, surpassing PMS. Overall, heterogeneous oxidation accelerated the oxidation kinetics of the PMS@Cl2 system by 1.1-2 orders of magnitude relative to the homogeneous oxidation of Cl2 alone. We here demonstrated that PMS@Cl2 could offer a more efficient mean of soluble Mn(II) mitigation, achieved with a relatively low routine dose of oxidant in a short reaction period. The outcomes of this study would address the existing limitations of traditional chlorine oxidation, minimizing the trade-offs associated with high residual chlorine levels after treatments for soluble manganese-containing water.

Efficient degradation of haloacetic acids by vacuum ultraviolet-activated peroxymonosulfate: Kinetics, mechanisms and theoretical calculations.

Efficient degradation of haloacetic acids (HAAs) is crucial due to their potential risks. This study firstly proposed vacuum ultraviolet - activated peroxymonosulfate (VUV/PMS) to remove HAAs (i.e., monochloroacetic acid (MCAA), monobromoacetic acid (MBAA), dichloroacetic acid (DCAA), etc). VUV/PMS achieved 99.51 % MCAA and 63.29 % TOC removal within 10 min. Electron paramagnetic resonance (EPR), quenching and probe experiments demonstrated that •OH was responsible for MCAA degradation. MCAA degradation followed pathways of dehalogenation (major) and decarboxylation (minor). VUV/PMS showed application potential under various reaction parameters. Broad spectrum of VUV/PMS on various HAAs was further explored. Chlorinated HAAs (Cl-HAAs) were primarily degraded by oxidation reactions, while brominated HAAs (Br-HAAs) by direct VUV photolysis. The density functional theory-based calculations (DFT) revealed that reaction rates of HAAs correlated with the highest occupied molecular orbital (HOMO) and energy gap (ΔE), indicating that HAAs degradation depends on their chemical structures. The Fukui function (f0 values) and bond length showed vulnerability of the halogen atom in Cl-HAAs and C-Br bond in Br-HAAs. Overall, this study provides an in-depth perspective on the oxidation performance and mechanism of HAAs using VUV/PMS. It not only demonstrates a green and efficient method but also inspires new strategies for HAAs remediation.