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.

A green edge-hosted zinc single-site heterogeneous catalyst for superior Fenton-like activity.

Developing green heterogeneous catalysts with excellent Fenton-like activity is critical for water remediation technologies. However, current catalysts often rely on toxic transitional metals, and their catalytic performance is far from satisfactory as alternatives of homogeneous Fenton-like catalysts. In this study, a green catalyst based on Zn single-atom was prepared in an ammonium atmosphere using ZIF-8 as a precursor. Multiple characterization analyses provided evidence that abundant intrinsic defects due to the edge sites were created, leading to the formation of a thermally stable edge-hosted Zn-N4 single-atom catalyst (ZnN4-Edge). Density functional theory calculations revealed that the edge sites equipped the single-atom Zn with a super catalytic performance, which not only promoted decomposition of peroxide molecule (HSO5-) but also greatly lowered the activation barrier for •OH generation. Consequently, the as-prepared ZnN4-Edge exhibited extremely high Fenton-like performance in oxidation and mineralization of phenol as a representative organic contaminant in a wide range of pH, realizing its quick detoxification. The atom-utilization efficiency of the ZnN4-Edge was ~104 higher than an equivalent amount of the control sample without edge sites (ZnN4), and the turnover frequency was ~103 times of the typical benchmark of homogeneous catalyst (Co2+). This study opens up a revolutionary way to rationally design and optimize heterogeneous catalysts to homogeneous catalytic performance for Fenton-like application.

Revealing *OOH key intermediates and regulating H2O2 photoactivation by surface relaxation of Fenton-like catalysts.

Hydrogen peroxide (H2O2) molecules play important roles in many green chemical reactions. However, the high activation energy limits their application efficiency, and there is still huge controversy about the activation path of H2O2 molecules over the presence of *OOH intermediates. Here, we confirmed the formation of the key species *OOH in the heterogeneous system, via in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), isotope labeling, and theoretical calculation. In addition, we found that compared with *H2O2, *OOH was more conducive to the charge transfer behavior with the catalyst and the activation of an O-O bond. Furthermore, we proposed to improve the local coordination structure and electronic density of the YFeO3 catalyst by regulating the surface relaxation with Ti modification so as to reduce the activation barrier of H2O2 and to improve the production efficiency of •OH. As a result, the kinetics rates of the Fenton-like (photo-Fenton) reaction had been significantly increased several times. The •OH free radical activity mechanism and molecular transformation pathways of 4-chloro phenol (4-CP) were also revealed. This may provide a clearer vision for the further study of H2O2 activation and suggest a means of designing catalysts for efficient H2O2 activation.

Identification of Fenton-like active Cu sites by heteroatom modulation of electronic density.

Developing heterogeneous catalysts with atomically dispersed active sites is vital to boost peroxymonosulfate (PMS) activation for Fenton-like activity, but how to controllably adjust the electronic configuration of metal centers to further improve the activation kinetics still remains a great challenge. Herein, we report a systematic investigation into heteroatom-doped engineering for tuning the electronic structure of Cu-N4 sites by integrating electron-deficient boron (B) or electron-rich phosphorus (P) heteroatoms into carbon substrate for PMS activation. The electron-depleted Cu-N4/C-B is found to exhibit the most active oxidation capacity among the prepared Cu-N4 single-atom catalysts, which is at the top rankings of the Cu-based catalysts and is superior to most of the state-of-the-art heterogeneous Fenton-like catalysts. Conversely, the electron-enriched Cu-N4/C-P induces a decrease in PMS activation. Both experimental results and theoretical simulations unravel that the long-range interaction with B atoms decreases the electronic density of Cu active sites and down-shifts the d-band center, and thereby optimizes the adsorption energy for PMS activation. This study provides an approach to finely control the electronic structure of Cu-N4 sites at the atomic level and is expected to guide the design of smart Fenton-like catalysts.

Rape Straw Supported FeS Nanoparticles with Encapsulated Structure as Peroxymonosulfate and Hydrogen Peroxide Activators for Enhanced Oxytetracycline Degradation.

Iron-based catalysts with high load content of iron sulfide (FeS) were commonly peroxymonosulfate (PMS) and hydrogen peroxide (H2O2) activators to degrade organic pollutants but limited catalytic efficiency and increased risk of ferrous ion leaching restricted their use. Meanwhile, various biomass materials such as straw, peel, and branch have been extensively prepared into biochar for mechanical support for iron-based catalysts; however, the preparation process of biochar was energy-intensive. In this study, FeS nanoparticles modified rape straw composites (RS-FeS) encapsulated with ethylenediaminetetraacetic acid (RS-EDTA-FeS) were successfully presented by in-situ synthesis method for efficiently activating PMS and H2O2 to degrade oxytetracycline (OTC), which was economical and environmentally friendly. The results showed that the modified rape straw can remove OTC efficiently, and the addition of EDTA also significantly enhanced the stability and the reusability of the catalyst. In addition, EDTA also promoted the activation of H2O2 at neutral pH. The OTC degradation efficiency of the two catalysts by PMS was faster than that of H2O2, but H2O2 had a stronger ability to remove OTC than PMS. The highest OTC removal efficiency of RS-FeS and RS-EDTA-FeS were 87.51 and 81.15%. O2•- and 1O2 were the major reactive oxidative species (ROS) in the PMS system. Furthermore, compared with RS-FeS, the addition of EDTA inhabited the generation of O2•- in the PMS system. Instead, O2•- and •OH were the major ROS in the H2O2 system, but 1O2 was also identified in RS-FeS/H2O2 system. RS-EDTA-FeS showed a trend of rising first and then decreasing in recycle test. Instead, the removal rate of OTC by RS-FeS decreased significantly with the increase in reuse times. In the actual wastewater test, the TOC removal of two catalysts active by H2O2 was better than PMS, which was consistent with the test results of OTC, indicating that the two catalysts have application value in the removal of organic pollutants in actual wastewater. This study directly used plant materials as catalysts and omits the preparation process of biochar, greatly reduces the preparation cost and secondary pollution of catalysts, and provides theoretical support for the deepening of advanced oxidation technology.

Removal of refractory organics from landfill leachate by in situ electrogenerated H2O2 combined with an Fe0 Fenton-like process.

Landfill leachate contains a large amount of refractory organic matter, which will cause harm to the environment if not appropriately treated. In this study, the refractory organic matter in landfill leachate has been treated by in situ electrogenerated H2O2 combined with an Fe0 Fenton-like process, aiming to explore a cleaner and more efficient process for leachate treatment. The results showed that the current, initial pH and oxygen flow rate have significant influences on H2O2 production. The current and oxygen flow rate are positively correlated with H2O2 production, and neutral conditions are more favourable. Under the conditions of a current of 200 mA, an initial pH of 7.0 and an oxygen flow rate of 0.3 L/min, H2O2 production reached 2.81 mM, the current efficiency was close to 80% and the highest removal efficiency of organic matter reached 40.70%. The absorbance at 280 nm (E280) decreased from 0.1669 to 0.1180, and the ratios E240/E420, E250/E365 and E300/E400 in the UV and visible regions changed from 0.7825, 5.4492 and 0.2422 to 1.3135, 7.3745 and 0.2966, respectively. The maximum fluorescence intensities due to humic-like acid and fulvic-like acid substances decreased from 1275 and 1246 to 595.9 and 711.0, respectively. Spectral analysis further showed that the complex structure of refractory organic matter in the landfill leachate was obviously destroyed, and the relative content of humus decreased significantly. This study may provide a theoretical basis for the effective treatment of refractory organic matter in landfill leachate by in situ electrogenerated H2O2 combined with a Fenton-like process.

Self-Accelerating Interfacial Catalytic Elimination of Gaseous Sulfur-Containing Volatile Organic Compounds as Microbubbles in a Facet-Engineered Three-Dimensional BiOCl Sponge Fenton-Like Process.

The elimination of gaseous sulfur-containing volatile organic compounds (S-VOCs) by a microbubble-assisted Fenton-like process is an innovative strategy. Herein, we established a microbubble-assisted Fenton-like process to eliminate malodorous microbubble CH3SH as representative gaseous S-VOCs, in which BiOCl nanosheets loaded on a three-dimensional sponge were exposed to (001) or (010) facets and induced Fenton-like interface reactions. Intriguingly, the microbubble-assisted Fenton-like process significantly removed 99.9% of CH3SH, higher than that of the macrobubble-assisted Fenton-like process (39.0%). The self-accelerating interfacial catalytic mechanism was in-depth identified by in situ ATR-FTIR, PTR-TOF-MS, EPR, and DFT computational study. The extraordinary elimination performance of microbubble-assisted Fenton-like process lies in the enhancing dissolution/mass transfer of gaseous CH3SH in the gas/liquid phase and the tight contact between CH3SH-microbubbles and 3D-BiOCl sponge due to the low rising velocity (0.13 mm s-1) and negative charge (-45.53 mV) of CH3SH-microbubbles, as well as the effective generation of 1O2 by activating the enriched dissolved oxygen in CH3SH-microbubble via effective electron-polarized sites on 3D-BiOCl sponge. Furthermore, CH3SH-microbubbles transferred electrons to H2O2 through electron-rich oxygen vacancy centers of the 3D-BiOCl sponge to generate more •OH, thus achieving excellent elimination performance. Overall, this study demonstrates the enhanced self-accelerating interfacial catalytic elimination by S-VOC microbubble and provides the underlying mechanisms.

Synthetic Fe-rich nontronite as a novel activator of bisulfite for the efficient removal of tetracycline.

In this work, the iron-containing smectite nontronite (NNT) was artificially prepared by hydrothermal process and used as a heterogeneous catalyst to activate bisulfite (BS) for degradation of tetracycline (TC). Two NNT samples with different iron content (NNT1 and NNT2) were characterized by XRD, FTIR, XPS and SEM-EDS analysis. Under dark condition, the TC removal rates of NNT1/BS and NNT2/BS reached about 91.7% and 95.5% respectively at 60 min. Due to the heterogeneous catalysis of structural Fe(III), the NNT catalysts showed great catalytic activity and low iron leaching at the pH range 3.0-7.5. In addition, NNT particles were also stable and reusable in activating BS for TC removal. According to the EPR and radical quenching experiments, it could be proved that the precursor radical •SO3- was first generated in NNT/BS system, then •SO4- and •OH were the active species that played a role in TC degradation. The synthetic NNT clay is a promising Fe-based catalyst for treatment of TC wastewater thanks to its high activity, good stability and effective reusability.

Photo-Fenton-like degradation of bisphenol A by persulfate and solar irradiation.

This work evaluates the feasibility of a solar-enhanced Fenton-like process using S2O82- (PS) and Fe2+ for the elimination of BPA, a model endocrine-disruption compound. This comparative study of BPA removal showed that among the approaches employed, the effectiveness of BPA degradation (10 mg/L) decreased in the order: Solar/PS/Fe2+> Solar/PS > PS/Fe2+> Solar/Fe2+> Solar. The complete degradation of BPA was achieved by Solar/PS/Fe2+ treatment at a [PS]:[BPA] ratio of 20 in less than t30W 5 in deionised water. The high efficiency of the Solar/PS/Fe2+ process revealed a synergistic effect (ϕ = 2.38) between the applied activation agents on the formation of reactive oxygen species (ROS) and subsequent decomposition of BPA. The treatment was accompanied by total organic carbon (TOC) removal (44%) in 45 min. Sequential generation of reactive oxygen species has made Solar/PS/Fe2+ a kinetically effective process for removing BPA without accumulation of toxic intermediates. The reaction rate followed pseudo-first-order kinetics that increased with increasing PS and Fe2+ concentrations. Experimental evidence suggests that exposure to solar irradiation maintains suitable quantities of free Fe2+ in the reaction mixture, even at low catalyst concentrations (the molar ratio of [PS]:[Fe2+] varied from 1:0.01 to 1:0.08). The effects of HCO3-, SO42-, and Cl- were also examined. As expected, HCO3- and SO42- inhibited BPA oxidation. The effect of Cl- on the oxidation efficiency of BPA in Fenton-like systems depends not only on actual Cl- concentrations but it is also highly influenced by molar ratios of Cl- to oxidant and catalyst. Inhibition, which was caused by Cl- in the mM range can be overcome by prolonging the reaction time or increasing the initial Fe2+concentration. Finally, the efficiency of Solar/PS/Fe2+ process was examined in diluted natural surface water and wastewater effluent. On eliminating the buffering action of HCO3-/CO32- ions by lowering the pH value to 4.5, complete BPA degradation was achieved in all real water matrices.

Removal of sulfamethazine antibiotics using CeFe-graphene nanocomposite as catalyst by Fenton-like process.

The presence of sulfonamide (SMT) antibiotics in aquatic environments has received increasing attention in recent years, and they are ubiquitous pollutants which cannot be effectively removed by conventional wastewater treatment processes. In this paper, the nanocomposites Ce(0)/Fe(0)-reduced graphene oxide (Ce(0)/Fe(0)-RGO) were synthesized through chemical reduction method, and characterized by Raman and FTIR before and after use. The addition of RGO can prevent the agglomeration of Ce(0) and Fe(0). The elimination of SMT can be divided into adsorption and degradation process. The adsorption of SMT onto the catalyst can enhance its degradation. The effect of pH value, concentration of H2O2, catalyst dosage, temperature and initial SMT concentration on the removal efficiency of SMT was determined. When pH = 7, T = 25 °C, H2O2 = 8 mM, Ce(0)/Fe(0)-RGO = 0.5 g/L, SMT = 20 mg/L, the removal efficiency of SMT and TOC was 99% and 73%, respectively. The stability of the catalysts was evaluated with repeated batch experiments using ethanol, water and acid as solvents to wash the used catalysts, respectively. The surface change of the catalysts after each use was characterized by Raman and FTIR analysis. The intermediates were detected by GC-MS and IC, the possible degradation pathway of SMT was tentatively proposed.

Radical-driven selective oxidation of benzyl alcohol on MnCoOx catalysts with no oxidant other than air in reactor.

Mn reinforced Co3O4 catalysts (MnCoOx) were prepared by a facile solid phase mixed foaming method with an in-situ heating enhancement for the formation of spinel phase mixed oxide species, and studied in the selective oxidation of benzyl alcohol just the air in reactor as oxygen donor. It was found that the MnCoOx catalysts are composed of relatively minimal spinel MnCo2O4 mixed oxide and massive Co3O4 to form MnCo2O4-Co3O4 oxide pair. The micro-domains of MnCo2O4-Co3O4 oxide pair present two redox couples of Mn3+/Mn2+ and Co3+/Co2+ instead of the single one of Co3+/Co2+ in Co3O4, and then dramatically enhance the formation of superoxide radicals (•O2-) species from the O2 in air, which can efficiently initiate the conversion of benzyl alcohol to benzaldehyde in a Fenton-like processes. With no oxidant other than air in reactor, the interaction between MnCo2O4 and Co3O4 in MnCoOx catalysts leads to a benzyl alcohol conversion up to 98 % with a 100 % benzaldehyde selectivity at atmospheric pressure while single component Co3O4 can only present a benzyl alcohol conversion at 37 %. This embodiment of highly efficient heterogeneous selective oxidation just with air as oxidant provides a probability for developing a low-cost and super-facile radical-induced selective oxidation process for alcohols.

Effects of Fe3O4 NMs based Fenton-like reactions on biodegradable plastic bags in compost: New insight into plastisphere community succession, co-composting efficiency and free radical in situ aging theory.

Biodegradable plastic bags (BPBs), meant for eco-friendly, often inadequately degrade in compost, leading to microplastic pollution. In this study, the effect of Fenton-like reaction with Fe3O4 nanoparticles (NMs) on the plastisphere microorganisms' evolution and the BPBs' aging mechanism was revealed by co-composting of food waste with BPBs for 40 days. The establishment of the Fenton-like reaction was confirmed, with the addition of Fenton-like reagent treatments resulting in an increase of 57.67% and 37.75% in H2O2 levels during the composting, compared to the control group. Moreover, the structural characterization reveals that increasing oxygen content continuously generates reactive free radicals on the surface, leading to the formation of oxidative cavities. This process results in random chain-breaking, significantly reducing molecular weights by 39.27% and 38.81%, thus showcasing a deep-seated transformation in the plastic's molecular structure. Furthermore, the microbial network suggested that the Fenton-like reaction enriched plastisphere keystone species, thus accelerating the BPBs' aging. Additionally, the Fenton-like reaction improved compost maturity and reduced greenhouse gas emissions. These results reveal the bio-chemical mechanisms of BPBs aging and random chain-breaking by the Fenton-like reaction, under alternating oxidative/anoxic conditions of composting and provide a new insight to resolve the BPBs' pollutions.

Selective formation of high-valent iron in Fenton-like system for emerging contaminants degradation under near-neutral and high-salt conditions.

In view of the near-neutral and high-salt conditions, the Fenton technology with hydroxyl radicals (HO•) as the main reactive species is difficult to satisfy the removal of trace emerging contaminants (ECs) in pharmaceutical sewage. Here, a layered double hydroxide FeZn-LDH was prepared, and the selective formation of ≡Fe(IV)=O in Fenton-like system was accomplished by the chemical environment regulation of the iron sites and the pH control of the microregion. The introduced zinc can increase the length of Fe-O bond in the FeZn-LDH shell layer by 0.22 Å compared to that in Fe2O3, which was conducive to the oxygen transfer process between ≡Fe(III) and H2O2, resulting in the ≡Fe(IV)=O formation. Besides, the amphoteric hydroxide Zn(OH)2 can regulate the pH of the FeZn-LDH surface microregion, maintaining reaction pH at around 6.5-7.5, which could avoid the quenching of ≡Fe(IV)=O by H+. On the other hand, owing to the anti-interference of ≡Fe(IV)=O and the near-zero Zeta potential on the FeZn-LDH surface, the trace ECs can also be effectively degraded under high-salt conditions. Consequently, the process of ≡Fe(IV)=O generation in FeZn-LDH system can satisfy the efficient removal of ECs under near-neutral and high-salt conditions.

Piezoelectric catalytic driven advanced oxidation process using two-dimensional metal dichalcogenides for wastewater pollutants remediation.

The public and society have increasingly recognized numerous grave environmental issues, including water pollution, attributed to the rapid expansion of industrialization and agriculture. Renewable energy-driven catalytic advanced oxidation processes (AOPs) represent a green, sustainable, and environmentally friendly approach to meet the demands of environmental remediation. In this context, 2D transition metal dichalcogenides (TMDCs) piezoelectric materials, with their non-centrosymmetric crystal structure, exhibit unique features. They create dipole polarization, inducing a built-in electric field that generates polarized holes and electrons and triggers redox reactions, thereby facilitating the generation of reactive oxygen species for wastewater pollutant remediation. A broad spectrum of 2D TMDCs piezoelectric materials have been explored in self-integrated Fenton-like processes and persulfate activation processes. These materials offer a more simplistic and practical method than traditional approaches. Consequently, this review highlights recent advancements in 2D TMDCs piezoelectric catalysts and their roles in wastewater pollutant remediation through piezocatalytic-driven AOPs, such as Fenton-like processes and sulfate radicals-based oxidation processes.

Copper(II) phosphate as a promising catalyst for the degradation of ciprofloxacin via photo-assisted Fenton-like process.

This work aims to unravel the potential of copper(II) phosphate as a new promising heterogenous catalyst for the degradation of ciprofloxacin (CIP) in the presence of H2O2 and/or visible light (λ > 400 nm). For this purpose, copper(II) phosphate was prepared by a facile precipitation method and fully characterized. Of our particular interest was the elucidation of the kinetics of CIP degradation on the surface of this heterogeneous catalyst, identification of the main reactive oxygen species responsible for the oxidative degradation of CIP, and the evaluation of the degradation pathways of this model antibiotic pollutant. It was found that the degradation of the antibiotic proceeded according to the pseudo-first-order kinetics. Copper(II) phosphate exhibited ca. 7 times higher CIP degradation rate in a Fenton-like process than commercial CuO (0.00155 vs. 0.00023 min-1, respectively). Furthermore, the activity of this metal phosphate could be significantly improved upon exposure of the reaction medium to visible light (reaction rate = 0.00445 min-1). In a photo-assisted Fenton-like process, copper(II) phosphate exhibited the highest activity in CIP degradation from among all reference samples used in this study, including CuO, Fe2O3, CeO2 and other metal phosphates. The main active species responsible for the degradation of CIP were hydroxyl radicals.

A tartaric acid (TA)-coated iron-based biochar as heterogeneous fenton catalyst for enhanced degradation of dibutyl phthalate.

Iron-biochar composite is a promising catalyst in Fenton-like system for removal of organic pollutants. Nevertheless, low cycling rate of Fe(III)/Fe(II), high iron leaching and low H2O2 utilization efficiency impedes its application. Herein, a iron-based biochar (C-Fe) coated with tartaric acid (TA) was synthesized. The specific structure of inherent graphitized carbon and TA coating improved the removal efficiency of dibutyl phthalate (DBP) to 93%, promoted 2-fold increase in HO• production in H2O2 activation, improved the cycling rate of Fe(III)/Fe(II), and mitigated Fe leaching significantly. The developed HO• and 1O2 dominated Fenton-like system had an excellent pH universality and anti-interference to inorganic ions and real water matrixes. Moreover, C-Fe-TA has been shown to efficiently degrade DBP by using the dissolved oxygen in water to generate HO•. This work provided a novel insight for sustainable and efficient HO• and 1O2 generation, which motivated the development of new water treatment technology based on efficient iron-biochar catalyst.

Mesoporous TiO2 and Fe-containing TiO2 prepared by solution combustion synthesis as catalysts for the photodegradation of paracetamol.

Water pollution due to emerging contaminants, e.g., pharmaceuticals, is one of the most frequently discussed issues. Among them, paracetamol received great attention due to its physico-chemical properties, persistence, and adverse environmental effects. Different techniques were employed for its degradation and, among them, photodegradation is considered one of the most suitable to pursue the aim. This work aimed to synthesize mesoporous TiO2, even with the presence of iron, through a one-pot method, with an enhanced ability to abate paracetamol. Precisely, pure and iron-containing (3.5 wt%) TiO2 were successfully obtained employing an uncommon procedure for this kind of material, mainly solution combustion synthesis (SCS). Moreover, a traditional hydrothermal method and a commercial Degussa P25 were also investigated for comparison purposes. The samples were characterized through N2-physisorption at - 196 °C, XRD, XPS, EDX, DR UV-Vis, and FESEM analysis. The catalytic activity was investigated for the abatement of 10 ppm of paracetamol, under UV irradiation in acidic conditions (pH = 3) and in the presence of H2O2. As a whole, the best-performing catalysts were those obtained through the SCS procedure, highlighting a complete removal of the organic pollutant after 1 h in the case of Fe/TiO2_SCS, thanks to its highly defective structure and the presence of metal Fe. To better investigate the performance of both pure and Fe-containing SCS samples, further oxidation tests were performed at pH = 7 and in the absence of H2O2. Noteworthy, in these conditions, the two samples exhibited different behaviors, highlighting different mechanisms depending on the presence or absence of iron in the structure. Finally, a kinetic study was conducted, demonstrating that a first order is suitable for its abatement.

Interfacial OOH* mediated Fe(II) regeneration on the single atom Co-N-C catalyst for efficient Fenton-like processes.

Fe(II) regeneration is decisive for highly efficient H2O2-based Fenton-like processes, but the role of cobalt-containing reactive sites in promoting Fe(II) regeneration was overlooked. Herein, a single atom Co-N-C catalyst was employed in Fe(II)/H2O2 system to promote the degradation of diverse organic contaminants. The EPR and quenching experiments indicated Co-N-C significantly enhanced the generation of superoxide species, and accelerated hydroxyl radical generation for pollutant degradation. The electrochemical and surface composition analyses demonstrated the enhanced H2O2 activation and Fe(III)/Fe(II) recycling on the catalyst. Furthermore, in-situ Raman characterization with shell-isolated gold nanoparticles was employed to visualize the interfacial reactive intermediates and their time-resolved interaction. The accumulation of interfacial CoOOH* was confirmed when Co-N-C activated H2O2 alone, but it rapidly transformed into FeOOH* upon Fe(II) addition. Besides, the temporal variation of OOH* intermediates and the relative intensity of Co(III)-O and Co(IV)=O peaks depicted the dynamic interaction of reactive intermediates along the H2O2 consumption. With this basis, we proposed a mechanism of interfacial OOH* mediated Fe(II) regeneration, which overcame the kinetical limitation of Fe(II)/H2O2 system. Therefore, this study provided a primary effort to elucidate the overlooked role of interfacial CoOOH* in the Fenton-like processes, which may inspire the design of more efficient catalysts.

Fe-g-C3N4/reduced graphene oxide lightless application for efficient peroxymonosulfate activation and pollutant mineralization: Comprehensive exploration of reactive sites.

To overcome the shortcomings of homogeneous Fe ion activating peroxymonosulfate (PMS), such as high pH-dependence, limited cycling of Fe(III)/Fe(II) and sludge production, graphite carbon nitride (g-C3N4) is chosen as a support for Fe ions, and reduced graphene oxide (rGO) is employed to facilitate the electron transfer process, thereby enhancing catalysis. Herein, a ternary catalyst, Fe-g-C3N4/rGO, is first applied under lightless condition for PMS activation, which exhibits ideal performance for contaminant mineralization. 82.5 % of the total organic carbon (TOC) in 100 mL of 5 mg/L bis-phenol A (BPA) was removed within 20 min by the optimal catalyst named 30%rFe0.2CN, which shows a strong pH adaptability over the range of 3-11 compared with a common Fenton-like system. Moreover, the highly stable Fe-g-C3N4/rGO/PMS catalytic system resists complex water matrices, especially those with high turbidity. To unveil the mechanism of PMS activation and pollutant degradation, the physicochemical properties of the as-prepared catalysts are comprehensively characterized by multiple techniques. The Fe(III) contained in both the Fe-N group and α-Fe2O3 component of 30%rFe0.2CN not only directly reacts with PMS to produce sulfate radicals (SO4-) and hydroxyl radicals (OH), but also combines with PMS to form the essential [Fe(III)OOSO3]+ active complex, thereby generating superoxide radicals (O2-) and singlet oxygen (1O2). Among the various reactive oxidizing species, 1O2 plays an important role in pollutant removal, which is additionally generated by the CO moiety of the catalyst activating PMS as well as PMS self-oxidation, indicating the dominance of the non-radical pathway in the pollutant degradation process. Due to the advantages of high efficiency, wide pH adaptability and stability, the proposed lightless Fe-g-C3N4/rGO/PMS catalytic system represents a promising avenue for practical wastewater purification.

Catalytic degradation of crystal violet and methyl orange in heterogeneous Fenton-like processes.

Metals-loaded (Fe3+, Cu2+ and Zn2+) activated carbons (M@AC) with different loading ratios (0.1%, 0.5%, 1%, 5% and 10%) were prepared and employed for catalytic degradation of dye model compounds (crystal violet (CV) and methyl orange (MO)) in wastewater by heterogeneous Fenton-like technique. Compared with Cu@AC and Zn@AC, 0.5% Fe3+ loaded AC (0.5Fe@AC) had better catalytic activity for dyes degradation. The effects of dyes initial concentration, catalyst dosage, pH and hydrogen peroxide (H2O2) volume on the catalytic degradation process were investigated. Cyclic performance, stability of 0.5Fe@AC and iron leaching were explored. Degradation kinetics were well fitted to the pseudo-second-order model (Langmuir-Hinshelwood). Almost complete decolorization (99.7%) of 400 mg L-1 CV was achieved after 30 min reaction under the conditions of CV volume (30 mL), catalyst dosage (0.05 g), H2O2 volume (1 mL) and pH (7.7). Decolorization of MO reached 98.2% under the same conditions. The abilities of pyrolysis char (PC) of dyeing sludge (DS) and metal loaded carbon to remove dye pollutants were compared. The intermediate products were analyzed and the possible degradation pathway was proposed. This study provided an insight into catalytic degradation of triphenylmethane- and aromatic azo-based substances, and utilization of sludge char.