Peroxymonosulfate Activation Performance Research Articles

A highly-efficient peroxymonosulfate activator using a sewage sludge derived biochar supported cobalt oxide: Mechanism and characteristics

The application of biochar derived from sewage sludge (BS) in Fenton-like reactions for contaminant removal has attracted considerable attention. Herein, a BS-supported Co3O4 (BS-Co3O4) catalyst was synthesized using a simple two-step hydrothermal-calcination process to achieve highly efficient activation of peroxymonosulfate (PMS). The introduction of biochar effectively inhibited the aggregation of Co3O4 and reduced cobalt leaching. Compared to Co3O4, the mesoporous BS-Co3O4 exhibited an 8-fold increase in specific surface area (SSA) to 111.92 m2∙g−1, and a 46 %-66.4 % reduction in crystal plane size. The interaction between biochar and cobalt oxide resulted in several notable enhancements in the BS-Co3O4 composite. Specifically, there was an increase in sp2 carbon content, a 42.69 % rise in capacitance, and a 79.99 % reduction in charge transfer resistance. These improvements contributed to enhanced PMS activation performance. The BS-Co3O4 also contained a higher content of Co(II), sp2 carbon, and oxygen vacancies (OV). Co(II) played a crucial role in the redox reaction, accelerating the formation of SO4•− and 1O2 during the PMS activation process. Additionally, OV acted as electron capture centers, further promoting the generation of 1O2. Evidence from reactive species investigations and electron paramagnetic resonance (EPR) tests indicated that SO4•− and 1O2 were the main reactive radicals for eliminating tetracycline (TC). Based on the identification of TC intermediates, two potential degradation pathways were proposed, and a reduction in intermediate toxicity was observed. Experiments involving interference and repetition demonstrated that the BS-Co3O4 catalyst was stable and reusable. This work provides a solution with low metal leaching, high recycling performance, and safety for antibiotic wastewater treatment.

An efficient peroxymonosulfate activator derived from metal-organic frameworks: The application of Cu, Mg co-doping strategy

The application of metal-organic frameworks (MOFs)-based catalysts in Fenton-like reactions attracts increasing attention, however, improving the efficiency of these catalysts remains a challenge. Herein, a highly efficient peroxymonosulfate (PMS) activator (CuMg@Fe-MOFs-500) derived from MOFs was successfully synthesized. The results indicated that the Cu and Mg co-doping strategy employed in the fabrication of CuMg@Fe-MOFs-500 significantly enhanced the PMS activation performance, achieving a tetracycline (TC) degradation efficiency of 96.8 % within 60 min. The incorporation of the doped Mg and Cu significantly increased the contents of the oxygen vacancy (OV) and low-valent copper (Cu0 and Cu+), respectively. The interaction between the OV and Cu0/Cu+ became a key factor during the PMS decomposition process. Furthermore, for the first time, the OV content was observed to be positively and negatively linearly correlated with the reaction rate constant (k) and the charge transfer resistance (Rct) of the prepared PMS activators, respectively. Quenching experiments and electron paramagnetic resonance (EPR) tests demonstrated that the predominant reactive species generated during the PMS activation process were SO4•-, •OH, O2•-, and 1O2. It was also shown that the 1O2 primarily originated from O2•- disproportionation, and a self-quenching process between SO4•- and •OH was also observed. The intermediates produced during pollutant degradation induced by PMS-based Fenton-Like reaction exhibited reduced toxicity, as demonstrated by ecotoxicity analysis. This study presented a novel approach for the fabrication of catalyst derived from bimetallic doped MOFs, characterized by a high OV content, for the application in PMS-based Fenton-like reactions.

Mechanisms and degradation pathways of tetracycline by Co7Fe3 nanoparticles anchored porous carbon activated peroxymonosulfate

In recent years, catalysts based on transition metals have been extensively employed for the activation of peroxymonosulfate (PMS) in the removal of tetracycline (TC) from aquatic environments. However, the efficiency of single transition metals and heterogeneous transition metals as catalysts has been somewhat limited. In this study, different bimetallic Co-Fe catalysts embedded in a porous carbon (Co7Fe3-500/600/700/800) were synthesized using a straightforward single-step calcination process at varying temperatures, addressing the issues of poor activation performance of single transition metals and low dispersion of active components in heterogeneous transition metals. The Co7Fe3-500/600/700/800 enhanced the electronic configuration, establishing electron-rich and highly active zones that promoted electron transfer between the Co and Fe transition metals. The results showed that Co7Fe3-600, exhibited excellent PMS activation performance, removing 95.1 % of TC from the solution within 10 min. Additionally, Co7Fe3-600 showed strong adaptability and resistance to interference under various environmental conditions. DFT calculations, HPLC-MS analysis and T.E.S.T analysis were used to predict potential degradation intermediates during TC degradation and assess their biological toxicity. This research introduces an innovative strategy for formulating sophisticated bimetallic alloy catalysts and contributes fresh perspectives on the mechanisms involved in the PMS activation process by bimetallic catalysts.

Mechanistic insights and performance evaluation of ZnFe-Modified bovine manure biochar in activating peroxymonosulfate for efficient thiamethoxam degradation: A combined DFT calculation and degradation pathway analysis

The study explored the degradation of thiamethoxam (THM) in water using modified bovine manure biochar as a catalyst for the first time, due to its potential harm to living organisms and frequent detection in natural water bodies. Experimental findings revealed that the rate constants for peroxymonosulfate (PMS)-catalyzed THM degradation by bovine manure biochar modified with ZnCl2 and K2FeO4 (ZnFeBC) increased by 76.78 times compared to unmodified biochar (BC), achieving a 100% degradation rate within 60 min. ZnFeBC exhibited excellent PMS activation performance across various pH levels. XPS characterization and Density Functional Theory (DFT) calculations have revealed that Fe element cycling occurs on the ZnFeBC surface, resulting in increased charge transfer rates at the reaction interface. The main active sites responsible for PMS activation were found to be Fe0 and Fe3O4. The degradation mechanism of THM by the ZnFeBC/PMS system involved SO4•-, •OH, 1O2 and electron transfer. This catalyst demonstrated strong pH adaptability and outstanding catalytic degradation capabilities for various pollutants, making it highly suitable for widespread wastewater treatment applications, while also providing a new way for resource reutilization of bovine manure.

Fast diffusion kinetics improves electron transfer regime selectivity to boost peroxymonosulfate activation

Electron transfer process (ETP) is barely influenced by half-life and migration distance in peroxymonosulfate (PMS) activation because it directly extracts electrons from pollutants for oxidation. However, the enhanced ETP selectivity is still challenging due to the poor mass transfer of PMS and pollutant. In this work, 2D porous N-doped carbon (PNC) with high reactant diffusion kinetics and multiple diffusion modes was designed to induce the interlayer confinement for efficient PMS activation with elevated ETP selectivity. Taking tetrabromobisphenol A as target pollutant, the confined PNC/PMS system achieved significantly enhanced PMS activation performance with the selectivity of ETP up to 97.8%. The vertical mass transfer of reactants into the inner interlayer space of the catalysts was proved to be promoted by the construction of molecule tunnels according to a diffusion model. Density functional theory calculations indicated that the subsequently triggered interlayer confinement facilitated the co-adsorption of PMS/pollutant on the interlayer surface and narrowed the energy gap of charge migration, resulting in enhanced PMS activation performance and ETP selectivity. Benefiting from the almost 100 % ETP selectivity, the confined PNC/PMS system exhibited substantially increased PMS utilization efficiency, admirable anti-interference ability towards various water matrices as well as long-term stability in a continuous-flow reactor. This work provides a new protocol for efficient and selective PMS activation by interlayer confinement in water remediation.

Synergistic combination of Mn/Fe bimetal-doped carbon nitride and peroxymonosulfate for efficient photocatalytic degradation of antibiotics

The widespread of antibiotics has resulted in potential threats to the aquatic environment and human health. The visible light-assisted peroxymonosulfate (PMS) activation method is considered to be an effective way to remove antibiotics in wastewater. In this study, Mn/Fe bimetal doped graphitic carbon nitride (MnFe-CN-x) was first synthesized for PMS activation under visible light towards tetracycline (TC) removal. The optimized MnFe-CN-50 possessed the excellent photocatalytic activity, PMS activation performance and photo-Fenton-like synergistic effect. In the photo-Fenton-like system, TC (20 mg L−1) was degraded by 99 % in 50 min and the kinetic constant was 0.074 min−1. The high dispersion of Mn and Fe in carbon nitride inhibited the recombination of charge carriers in MnFe-CN-x, increased its photocurrent density and charge mobility, effectively optimized the electronic structure, and promoted the generation of 1O2. Based on the analytical results of predictive toxicity evaluation software (TEST), it was confirmed that MnFe-CN-x could effectively reduce the environmental risks associated with antibiotic contamination. This study provided new insights into synthesizing bimetal-doped graphitic carbon nitride and the use of synergistic effects of photocatalysis and PMS activation to remove organic pollutants from wastewater.

Biochar assisted synthesis of α-MnO2 nanowires with superior performance for non-radical activation of peroxymonosulfate

Non-radical activation of peroxymonosulfate (PMS) is a promising water treatment technology for removing refractory organics, but its mechanism is still ambiguous and the development of highly efficient catalyst is still a challenge. Herein, α-MnO2 nanowires were synthesized by a hydrothermal method with the assistance of biochar and their performance for PMS activation was studied. The characterization results show that the addition of biochar had little effect on the crystal phase and valence state of MnO2 but significantly reduced the size of nanowires. These nanowires had mesoporous structure, high surface area and oxidation ability, resulting in their superior performance for removing organic pollutants with PMS activation. The degradation of phenol by α-MnO2-PMS followed first order kinetics with an activation energy of 14.82 kJ mol−1. Electron paramagnetic resonance and radical scavenging experiments demonstrated that this activation process followed the non-radical mechanism. The quenching effect of scavengers led to the misleading role of singlet oxygen. In fact, surface activated PMS (MnO2–PMS*) rather than singlet oxygen was the reactive species. Weak acidic condition was conducive for the formation of MnO2–PMS* complexes. This catalyst exhibited good reusability and high activity for removing various organic pollutants, and the common substances in real water had little effect on its performance, suggesting its potential application in wastewater treatment.

Electrochemically-induced metal–oxygen bond Cu(II)-[rad]SO5− on novel CuBi2O4 anode for efficient peroxymonosulfate activation

Transition metal oxide catalysts had the limitation of a slow electron transfer rate in activating peroxymonosulfate (PMS) during wastewater treatment. In this work, we developed a novel copper bismuthate (CuBi2O4) anode using a catalyst drop casting method to efficiently activate PMS through electrochemically induced metal–oxygen bonds for herbicide prometon (PMT) degradation. The PMT removal rate in the EC/CuBi2O4 anode/PMS system was 74.60 %, which was much greater than the simple superposition of CuBi2O4 catalyst-activated PMS alone (4.88 %) and FTO anode electrically activated PMS (32.15 %). The CuBi2O4 fixed on the anode surface accelerated the electron transfer efficiency between the interface employing the electric field, showing stronger PMS activation performance than the equivalent three-dimensional particle electrode system. The free radical quenching experiments illustrated that the degradation of PMT mainly proceeded through the free radical oxidation pathway dominated by SO4− and OH. In the EC/CuBi2O4 anode/PMS system, the traditional Cu+/Cu2+ cycle did not dominate the activation of PMS in the CuBi2O4 anode reaction. Raman experiment and open circuit potential results proved that the introduction of an electric field caused PMS to form the metal–oxygen bond Cu(II)-SO5− at the CuBi2O4 anode interface, and converted it into activated state PMS (PMS*), accelerating the interface electron transfer. The PMS* was more readily further activated by electrons and promoted water dissociation to form OH for pollutants degradation. The EC/CuBi2O4 anode/PMS system manifested stable purification performance for COD and emerging pollutants in high-salt pesticide wastewater, coupled with its superior economic benefits, possessing broad application prospects.

The overlooked role of different Fe-N4Cx configuration in single atom catalyst for efficient peroxymonosulfate activation

The coordination environment between the metal center and ligands in single atom catalysts (SACs) is a curial factor influencing their catalytic activity. Herein, two types of Fe-centered SACs were synthesized for peroxymonosulfate (PMS) activation. The result showed that SACs enriched with pyrrolic ligands (Fe-N4C12) exhibited significantly higher PMS activation performance compared to those with pyridinic ligands (Fe-N4C10). Density functional theory (DFT) calculations revealed that electron delocalization in pyrrolic ligands is more effective, rendering a stronger reactivity of Fe in Fe-N4C12. The adsorption of PMS onto Fe-N4 sites regulated the ligand field surrounding Fe from a square planar to a pseudo-octahedral field, thereby significantly activating the delocalization orbital. Pyrrolic ligands further maintained a lower d‐band center of Fe in the Fe-N4C12 configuration than Fe-N4C10 by pyridinic ligand. This led to a higher electron occupancy in antibonding band of Fe-N4C12 when PMS was adsorbed, and consequently, for better oxidation performance.

Boron and nitrogen hydrothermal co-doped sludge biochar towards efficiently activate peroxymonosulfate for sulfamethoxazole degradation

Designing efficient catalyst for peroxymonosulfate (PMS) activation is beneficial for eliminating the adverse effects of sulfamethoxazole (SMX) on human health. A novel boron (B) and nitrogen (N) co-doped sludge biochar (BNSBC) was synthesized by one-pot hydrothermal activation, and its remarkable PMS activation performance facilitated the rapid elimination of SMX from water. The degradation rate of SMX by BNSBC/PMS system could reach 92.1% within 60 min ([SMX]0 = 10 mg/L, [BNSBC]0 = 0.4 g/L, [PMS]0 = 1 mM). B and N exhibited the synergistic enhancement effects on the physico-chemical characteristics of SBC, and abundant pores, defects, CO, -O-B-O-, graphitic-N and pyridinic N were confirmed as the main active sites of BNSBC for PMS activation. Characterization, quenching, electron paramagnetic resonance (EPR) and electrochemical tests proved that non-radicals of surface-bound, 1O2 and electron transfer were the main contributors to SMX degradation. The high anti-interference of BNSBC/PMS system to pH range, co-existing inorganic anions and organic matter guaranteed its outstanding purification performance for SMX in diverse environmental waters. Four potential degradation pathways of SMX in BNSBC/PMS system were proposed by its intermediates identification and density functional theory (DFT) calculation, and pathway Ⅳ was the main one. The toxicity levels of its intermediates were lower than that of SMX regardless of chronic and acute toxicity. Also, BNSBC/PMS system exhibited the board-spectrum removal performance for other typical antibiotics (e.g., sulfadiazine (SDZ), sulfamethoxypyridazine (SMP), ciprofloxacin (CIP), tetracycline (TC)). BNSBC/PMS has great application potential for eliminating diverse antibiotics in actual wastewater due to its high tolerance to complex environmental conditions and outstanding detoxification ability, also it offers a harmless disposal approach for sludge.

Elucidating the mechanism on carbon nanotube-coated cobalt phosphide catalyst activating PMS to degrade norfloxacin contaminants

Transition metal phosphides have shown great potentials in persulfate activation for eliminating organic contaminants, while the understanding of the activation mechanism still remains fragmentary. Herein, a series of nitrogen-phosphorus-doped carbon nanotube-coated cobalt phosphide catalysts (Co/P-CNTs) were synthesized for activating peroxymonosulfate (PMS) to degrade norfloxacin (NOR). The optimal Co/P-CNTs-0.3 could eliminate NOR up to 97 % within 60 min in the presence of PMS. Results confirm that the synergistic interaction between multi-valent Co species in the Co/P-CNTs significantly contributes to the excellent PMS activation performance. The contribution of reactive oxygen species (ROS) to pollutant removal and the steady-state concentration of free radicals were quantitatively analyzed by means of chemical probe and reaction kinetics. A free radical mechanism dominated by SO4•– and NOR degradation pathway were identified, and the effect of coexisting inorganic anions was systematically evaluated. This study offers profound insights into the activation mechanism of metal phosphides towards environmental remediation.

Nanoarchitectonics of ternary Zn-Mn-Co oxides for efficient peroxymonosulfate activation and antibiotics degradation via accelerating electron transfer

In this work, a new nanoarchitectonics of ZnO/Mn3O4/Co3O4 (ZnMnCoO) was prepared by solvothermal and calcining processes, and used to degrade tetracycline (TC) with peroxymonosulfate (PMS) as oxidant. Coupling of trace Co3O4 (1.48 wt% Co) and difference in work functions of ZnO, Mn3O4, Co3O4 enabled ZnMnCoO to possess good PMS activation performance. 97.8% of TC was degraded in 30 min with reactive rate constant of 0.166 min–1, which was 2.6 and 1.4 times higher than those of Mn3O4/PMS and ZnO/Mn3O4/PMS systems, respectively. It was found that SO4•–, O2•−, 1O2, and complex-mediated electron transfer played the main roles in oxidizing TC. In addition, ZnMnCoO was attached to a polytetrafluoroethylene microfiltration membrane to degrade TC via a flow-through device, and 92.4% of TC (10 ppm TC, tap water) and 78.2% of total organic carbon were removed in 120 min. This study designs a novel composite with low Co content to efficiently activate PMS and degrade antibiotics.

High performance of reduced graphene oxide and g-C3N4 co-doped CuFe2O4 for peroxymonosulfate activation under visible light: Degradation process of sulfamethazine via a singlet oxygen dominated pathway

Peroxymonosulfate (PMS) activation by heterogeneous metal-based catalysts has been extensively applied for the degradation of organic pollutants in water. However, the catalysts suffer from the low oxidant utilization efficiency, pH limitations and severe matrix interference. Here, a reduced graphene oxide and g-C3N4 co-doped copper ferrite (rGO-CNCF) was synthesized and its performance for PMS activation under visible light was evaluated for removal of sulfamethazine. In the condition of rGO-CNCF (0.2 g/L) and PMS (0.1 g/L), the vis/rGO-CNCF/PMS system could degrade 99.9 % of sulfamethazine (SMT, 10 mg/L) within 30 min at pH 7.0, and the system also showed high degrading abilty of SMT over a wide pH range (0–14), along with a good adaptability to common coexisting ions in water solution. The introduction of rGO not only enhanced the stability of rGO-CNCF but also changed the binding sites between PMS and rGO-CNCF which reduced the adsorption energy. Singlet oxygen (1O2) was unveiled to be the major reactive oxygen species (ROS), which was produced by the transformation between negatively charged PMS (HSO5−) and water,along with the self-degradation of PMS. SMT was decomposed through four degradation pathways in this system, and quantitative structure–activity relationship (QSAR) predictions indicated a significant decrease in its toxicity. Results of this study indicated that the material can efficiently activate persulfate for the removal of organic pollutants from water under visible light conditions and it provided a novel catalytic system for removal of organic contaminants in water.

Electronic interaction between biochar and montmorillonite toward enhanced peroxymonosulfate activation

Biochar works as the catalyst for activating peroxymonosulfate (PMS) to produce highly oxidizing radicals to remove organic contaminants from wastewater, but its activity requires further improvement. Recent research demonstrates that the PMS activation performance of biochar is closely related to the oxygen-containing functional groups (OFGs). Therefore, biochar/montmorillonite (BC/Mt) composites are designed for activating PMS toward degrading tetracycline. The negative charge of Mt. induced the electron transfer form Mt. to BC, which increases the nucleophilicity of CO groups that promote the activation of PMS to •OH and SO4•− radicals. Meanwhile, the pyrolysis path of rice straw is tuned by Mt., and the amount of COO groups is increased from 8.99% to 9.79% that promotes the generation of 1O2. Moreover, electron paramagnetic resonance and quenching experiments reveal that the activation mechanism of PMS by the BC/Mt. is comprised of both the radical and the non-radical pathway. Consequently, the tetracycline degradation kinetics using the optimized BC/Mt. (0.117 min−1) is higher than either bare BC (0.0866 min−1) or bare Mt. (0.0258 min−1), highlighting the significance of the rational design of electrocatalysts toward the enhanced catalytic chemistry. This work provides a facile route to improve the catalytic performance of biochar by hybridizing with clay minerals and is of great significance to promote the practical application of PMS-based advanced oxidation processes.

Continuous flow degradation of Orange II by a dandelion-like NiCo2O4/NF activated peroxymonosulfate in a fixed-bed system

A novel dandelion-like catalyst, nickel foam supported NiCo2O4 (NiCo2O4/NF), was successfully synthesized and applied to the activation of peroxymonosulfate (PMS) in a fixed bed system for the degradation of Orange II (OII). The physicochemical properties of synthesis catalysts were identified by various characterization methods (SEM, EDS, XRD and XPS), revealing that the dandelion-like NiCo2O4 nanosheets were evenly distributed on the surface of NF. NiCo2O4/NF-250 showed excellent catalytic performance at a hydrothermal reaction time of 8 h, urea/metal ratio of 10:1, and Co/Ni concentration of 10 mM/5 mM. When PMS concentration was 5 mM, reaction temperature was 50 ℃, pH was 7.5, space velocity was 0.236 min−1, the conversion ratios of OII, PMS and COD were 99.8 %, 71.3 %, and 71.4 % at 240 min, respectively. In particular, NiCo2O4/NF still could reach 99.9 % OII conversion and 64.4 % COD conversion in the third cycle. DFT calculations implied that NiCo2O4/NF had excellent PMS activation performance.

Sludge-derived biochar applied in peroxymonosulfate (PMS) activation: Reactive oxygen species (ROS) dominated process and characteristics

Herein, sludge-derived biochar (BS) as an effective peroxymonosulfate (PMS) activator (BS900) was prepared by a simple one-step pyrolysis treatment. The BS900 demonstrated remarkable capability in activating PMS for efficient tetracycline (TC) removal. The existence of zero-valent iron (Fe0), the elevated ratio of Fe2+ to Fe3+, and the elevated percentage content of graphitic N were identified as the main contributors to the high PMS activation performance of BS900. Correspondingly, compared with other BS-derived PMS activators, the lowest charge transfer resistance (Rct) of BS900 was obtained, indicating efficient charge transfer between the PMS molecule and BS900. The generated reactive oxygen species (ROS) including the superoxide radical (O2•-) and singlet oxygen (1O2) were verified by the radical trapping and electron paramagnetic resonance (EPR) tests during the BS-induced PMS activation process. The generated O2•- served as the precursor for 1O2 formation. Whereas, the yields of the OH• and SO4•- were inhibited, suggesting that PMS activation by BS900 was a process dominated by ROS. Furthermore, the evaluation of ecotoxicity showed the TC degradation intermediates exhibit lower developmental toxicity and no mutagenicity. The research offers a novel perspective into the characteristics and mechanism of PMS-based advanced oxidation processes (AOPs) catalyzed by sludge-derived biochar.

Engineered hydrochar from waste reed straw for peroxymonosulfate activation to degrade quinclorac and improve solanaceae plants growth

Hydrochar from agricultural wastes is regarded as a prospective and low-cost material to activate peroxymonosulfate (PMS) for degrading pollutants. Herein, a novel in-situ N-doped hydrochar composite (RHCM4) was synthesized using montmorillonite and waste reed straw rich in nitrogen as pyrolysis catalyst and carbon source, respectively. The fabricated RHCM4 possessed excellent PMS activation performance for decomposing quinclorac (QC), a refractory herbicide, with a high removal efficiency of 100.0% and mineralization efficiency of 75.1%. The quenching experiments and electron spin resonance (ESR) detection disclosed free radicals (•OH, •SO4−, and •O2−) and non-radicals (1O2) took part in the QC degradation process. Additionally, the catalytic mechanisms were analyzed in depth with the aid of various characterizations. Moreover, the QC degradation intermediates and pathways were clarified by density functional theory calculations and HPLC-MS. Importantly, phytotoxicity experiments showed that RHCM4/PMS could efficaciously mitigate the injury of QC to Solanaceae crops (pepper, tomato, and tobacco). These findings give a new idea for enhancing the catalytic activity of hydrochar from agricultural wastes and broaden its application in the field of agricultural environment.

High efficient PMS activation by synergistic effects of bimetallic sulfide FeS2@MoS2 for rapid OFX degradation

Antibiotics have been widely used to treat bacterial diseases. Their wide spread in ecological environment will induce generation of antibiotic-resistant bacteria Therefore, it is critical to create an eco-friendly and effective approach for their removal. Herein, a bimetallic sulfide FeS2@MoS2 with rich sulfur vacancies (SVs) and high percentage of metallic 1T phase MoS2 was prepared by one-step solvothermal method to degrade ofloxacin (OFX) by activated peroxymonosulfate (PMS). FeS2@MoS2-1 (the mass ratio of Fe/Mo is 1) exhibited excellent performance for PMS activation, with 99.26% OFX removed in 20 min (0.2 g/L FeS2@MoS2-1, 0.2 mM PMS, initial pH). The degradation rate constant of kobs was 0.21 min−1 with FeS2@MoS2-1 system, which was about 4.88 and 22.91 times of FeS2/PMS and MoS2/PMS systems under the same experimental conditions respectively. In FeS2@MoS2-1, besides S2−, SVs would also accelerate Fe(III)/Fe(II) circulation through increasing the exposure of Mo(IV) active sites. Additionally, MoS2 transferred from the semi-conductive 2H phase to the metallic 1T phase, which could speed up electron transfer rate significantly. Quenching experiment and EPR test showed that SO4− and O2− were the main active oxygen species. Degradation pathway was proposed through the active sites identification by DFT calculations and intermediates detection by HPLC-MS analyzation. The results showed that OFX were vulnerable to be attacked and broke to form small molecular compounds through hydrogen loss, oxidative cracking, decarboxylation and demethylation four ways. In addition, their bio-toxicity was investigated and results showed that the toxic was diminished. This work indicated that the satisfactory universality, recyclability and stability enabled FeS2@MoS2-1 could be used as an efficient catalyst to activate PMS to degrade refractory organic pollutants in water.

Co3O4 decoration on iron-contained biochar composite fabricated by co-pyrolysis of red mud and spent coffee ground: A synergistic hybrid for Rhodamine B degradation via peroxymonosulfate activation

In this study, a composite was prepared by co-pyrolysis of red mud (RM) and spent coffee grounds (SCG). Then, cobalt was incorporated in the as-prepared RM/biochar composite (RMBC) and employed as the heterogeneous activator of peroxymonosulfate (PMS) for Rhodamine B (RhB) degradation. A temperature-programmed reaction and X-ray diffraction (XRD) measurements disclosed that the hematite (Fe2O3) phase in RM experienced a step-wise reduction to magnetite (Fe3O4) and Fe0 with increasing temperature during the co-pyrolysis of RM and SCG. The RMBC exhibited low performance for PMS activation to degrade RhB. However, incorporating 1.5 wt% Co can drastically improve the catalytic performance. The influence of initial pH, catalyst dosage, initial RhB concentrations, and temperature on the degradation efficiency was investigated. The quenching experiments combined with electron paramagnetic resonance analysis proved that the ·OH and SO•−4radicals, and 1O2 no-radical were the main reactive species for RhB degradation in the Co3O4/RMBC/PMS system.

Enhanced non-radical degradation of organic pollutants by peroxymonosulfate activation with Zr-Mn composite oxide

Non-radical activation of peroxymonosulfate (PMS) with MnOX can degrade organic pollutants more selectively. However, improving the performance of MnOX is still a challenge. In this work, a series of Zr-Mn composite oxides were synthesized by a hydrothermal method and characterized by various techniques. Their performance for PMS activation was studied using phenol and ofloxacin as the target pollutants. The characterization results show that the introduction of Zr into MnOX increased the oxygen mobility, while the surface area and surface oxygen content of the composite oxides decreased with increasing the content of Mn. The combination of Zr-Mn led to a synergistic effect for PMS activation and the sample (ZM2) with the Zr:Mn ratio of 1:1 exhibited the highest activity. This can be attributed to its high oxygen mobility, suggesting that the manipulation of oxygen mobility should be an effective strategy for improving the performance of PMS catalyst. Singlet oxygen was found to be the reactive species for pollutants degradation, and this process was barely affected by coexisting substances due to the non-radical mechanism. Moreover, ZM2 exhibited good stability and reusability, suggesting its potential application in wastewater treatment.