Boosting peroxymonosulfate activation via Fe-Cu bimetallic hollow nanoreactor derived from copper smelting slag for efficient degradation of organics: The dual role of Cu.

Valorization of iron-rich metallurgical slags in the construction of Fenton-like catalysts has an appealing potential from the perspective of sustainable development. For the first time, copper smelting slag (CSS) was utilized as the precursor to synthesize hollow sea urchin-like Fe-Cu nanoreactors (Cu1.5Fe1Si) to activate peroxymonosulfate (PMS) for chlortetracycline hydrochloride (CTC) degradation. The hyper-channels and nano-sized cavities were formed in the catalysts owing to the induction and modification of Cu, not only promoting the in-situ growth of silicates and the formation of cavities due to the etching of SiO2 microspheres, but also resulting the generation of nanotubes through the distortion and rotation of the nanosheets. It was found that 100 % CTC degradation rate can be achieved within 10 min for Cu1.5Fe1Si, 75 times higher than that of Cu0Fe1Si (0.0024 up to 0.18 M-1‧min-1). The unique nanoconfined microenvironment structure could enrich reactants in the catalyst cavities, prolong the residence time of molecules, and increase the utilization efficiency of active species. Density functional theory (DFT) calculations show that Cu1.5Fe1Si has strong adsorption energy and excellent electron transport capacity for PMS, and Fe-Fe sites are mainly responsible for the activation of PMS, while Cu assists in accelerating the Fe(II)/Fe(Ⅲ) cycle and promotes the catalytic efficiency. The excellent mineralization rate (83.32 % within 10 min) and efficient treatment of CTC in consecutive trials corroborated the high activity and stability of the Cu1.5Fe1Si. This work provides a new idea for the rational design of solid waste-based eco-friendly functional materials, aiming at consolidating their practical application in advanced wastewater treatment.

Synergistic Coordination in Cu Single-Atom Catalysts Enhances High-Valent Copper-Oxo Species for Efficient PMS Activation.

In the domain of heterogeneous catalytic activation of peroxymonosulfate (PMS), high-valent metal-oxo (HVMO) species are widely recognized as potent oxidants for the abatement of organic pollutants. However, the generation selectivity and efficiency of HVMO are often constrained by stringent requirements for catalyst adsorption sites and electron transfer efficiency. In this study, a single-atom catalyst, CuSA/CNP&S, is synthesized featuring multiple types (planar/axial) of heteroatom coordination via an H-bond-assisted self-assembly strategy. It is confirmed that CuN3 active centers with axial S coordination are uniformly distributed in a carbon matrix modified by planar P atoms. CuSA/CNP&S activated PMS to selectively generate Cu(III)═OH species as the primary reactive oxygen species (ROS). The pseudo-first-order kinetic rate for bisphenol A degradation reached 1.51 min-1, a 17.57-fold increase compared to the unmodified CuSA/CN catalyst. Additionally, the CuSA/CNP&S catalyst demonstrates high efficiency and durability in removing contaminants from various aqueous matrices. Theoretical calculations and experimental results indicate that the intrinsic electric field generated by distal planar P atoms enhances electron transfer efficiency within the carbon matrix. Meanwhile, axial S coordination elevates the d-band center and tunes the eg * band broadening of Cu, thereby enhancing the adsorption selectivity for the terminal oxygen of PMS. This multitype coordination synergistically mitigates the issues of low selectivity and yield of HVMO species.

Synthesis of MoS2@MoO3/(Cu+/g-C3N4) ternary composites with double S-scheme heterojunction for peroxymonosulfate activation exposing to visible light.

The construction of semiconductor heterojunction is an effective way for charge separation in photocatalytic degradation of pollutants. In this study, a novel MoS2@MoO3/(Cu+/g-C3N4) ternary composites (MMCCN) was prepared via a simple calcination method. The as-prepared composites exhibited exceptional performance in activating peroxymonosulfate (PMS) for the degradation of rhodamine B (RhB). The activity testing results indicated that 99.41 % of RhB (10 mg·L-1, 10 mL) was effectively removed by the synergistic effect of composites photocatalyst (0.1 g·L-1) and PMS (0.1 g·L-1) under visible light irradiation for 40 min. Its reaction rate constant exceeded that of Cu+/g-C3N4, MoO3 and MoS2 by a factor of 3.56, 17.30 and 11.73 times, respectively. The crystal structure, band gap and density of states (DOS) of the semiconductors were calculated according to the density functional theory (DFT). Free radical trapping tests and electron spin resonance spectroscopy validated that 1O2, O2- and h+ are primary reactive species participating in the decomposition of RhB. The ternary composites demonstrated good stability and maintained excellent degradation efficiency even across four reaction cycles. Furthermore, the activation mechanism and the intermediates produced during the decomposition course of RhB by MMCCN/PMS/vis system were analyzed and elucidated. A double S-scheme heterojunctions was responsible for efficient separation of photo-induced electron-hole pairs. This work presents a novel method in the construction of double S-scheme heterojunctions for PMS activation which is expected to find wide applications in wastewater treatment and environmental remediation.

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.

Sustainability-inspired upcycling of plastic waste into porous carbon nanobulks for water decontamination via peroxymonosulfate activation.

"White pollution" is regarded as one of the most serious problems in the natural environment. Thus greener recycling of plastic waste has attracted significant efforts in recent research. In this study, to kill two birds with one stone, a series of porous carbon nanobulks (PCNs) were synthesized from the pyrolysis of plastic waste (polyethylene terephthalate, PET) and inorganic salt (including NaHCO3, Na2CO3, NaCl, and ZnCl2) for sulfadiazine (SDZ) degradation via peroxymonosulfate (PMS) activation. PCNs-1 (co-calcinated from PET and NaHCO3) with a large number of CO and COOH active sites, which were in favor of PMS activation and electron transfer during the catalytic process, had shown the best catalytic activity for SDZ degradation. Significantly, PCNs-1 exhibited excellent universality, adaptability, and stability. The degradation pathways of SDZ were identified by the total content of organic carbon (TOC), and high-resolution mass spectrometry (HR-MS). The possible mechanism was proposed according to the anion effect, quenching experiments, electron paramagnetic resonance (EPR), and electrochemical analysis, indicating that radical (OH, SO4-, O2-) and non-radical (1O2 and e) species were the catalytically active species for SDZ decomposition in the PCNs-1/PMS system. Moreover, Ecological Structure-Activity-Relationship Model (ECOSAR) program and wheat seed cultivation experiments clearly demonstrated that the biotoxicity of SDZ could be effectively reduced by the PCNs-1/PMS system. Here we successfully upcycled plastic waste into high-value materials for efficient water decontamination.

Advanced carbo-catalytic degradation of antibiotics using conductive polymer-seaweed biochar composite: Exploring N/S functionalization and non-radical dynamics.

Polyaniline (PANI) and Saccharina Japanica seaweed (kelp) biochar (KBC) composites were synthesized in-situ through polymerization. This study presents a novel approach to the degradation of sulfamethoxazole (SMX), a prevalent antibiotic, using a PANI-KBC composite to activate peroxymonosulfate (PMS). Extensive characterizations of the PANI-KBC composite were conducted, resulting in successful synthesis, uniform distribution of PANI on the biochar surface, and the multifunctional role of PANI-KBC in SMX degradation. A removal efficiency of 97.24% for SMX (10 mg L-1) was attained in 60 min with PANI-KBC (0.1 g L-1) and PMS (1.0 mM) at pH 5.2, with PANI-KBC showing effectiveness (>92%) across a pH range of 3.0-9.0. In the degradation of SMX, both radical (SO4•- and •OH) and non-radical (1O2 and electron transfer) pathways are involved. The reaction processes are critically influenced by the roles of SO4•-, 1O2 and electron transfer mechanisms. It was suggested that pyrrolic N, oxidized sulfur (-C-SO2-C-), structural defects, and O-CO were implicated in the production of 1O2 and electron transfer processes, respectively, and a portion of 1O2 originated from the conversion of O2•-. The study evaluated by-product toxicity, composite reusability, and stability, confirming its practical potential for sustainable groundwater remediation.

Engineered digestate-derived biochar mediated peroxymonosulfate activation for oxytetracycline removal in sustainable wastewater remediation.

Nowadays, biochar is extensively used in wastewater remediation with the aim of achieving water security and circularity with minimal impacts on ecosystems and the environment. In this study, digestate biochar was prepared and modified using different methods and then employed as a peroxymonosulfate (PMS) activator to oxidize oxytetracycline, a model antibiotic pollutant in wastewater. The optimal biochar catalyst was characterized, spin trapping tests were carried out to confirm the dominant catalytic mechanism, and in silico toxicity prediction was conducted based on structure-activity relationships. Assessment of the catalytic performance of the pristine and engineered biochar showed that nitrogen doping increased oxytetracycline degradation efficiency by 1.92-fold (i.e., 100% oxytetracycline degradation with the engineered biochar compared to 52% with pristine biochar), while pyrrolic nitrogen was identified as a major PMS activation site. It was discovered that several parameters, such as catalyst dose, pH, PMS concentration, and competing ions, affected oxytetracycline degradation efficiencies. Additionally, the toxicity of the degradation intermediate was studied. Scavenger trapping tests showed that 1O2 and SO4•- were the most prevalent species during oxytetracycline degradation in the system, with four possible degradation pathways proposed, including secondary alcohol oxidation, hydroxylation, dehydration, and deamidation. Overall, it is anticipated that this study would contribute to our understanding of metal-free biochar activation of PMS as an attractive treatment scheme for antibiotic-polluted water.

Discerning the role of a site cation in ACoO3 perovskites for boosting Co3+/Co2+ redox cycle for pollutant degradation: DFT calculation, mechanism and toxicity evolution.

The degradation of persistent and refractory pollutants, particularly plastic and resins manufacturing wastewater, poses a significant challenge due to their high toxicity and high concentrations. This study developed a novel hybrid ACoO3 (A = La, Ce, Sr)/PMS perovskite system for the treatment of multicomponent (MCs; ACN, ACM and ACY) from synthetic resin manufacturing wastewater. Synthesized perovskites were characterized by various techniques i.e., BET, XRD, FESEM with EDAX, FTIR, TEM, XPS, EIS, and Tafel analysis. Perovskite LaCoO3 exhibited the highest degradation of MCs i.e., ACN (98.7%), ACM (86.3%), and ACY (56.4%), with consumption of PMS (95.2%) under the optimal operating conditions (LaCoO3 dose 0.8 g/L, PMS dose 2 g/L, pH 7.2 and reaction temperature 55 °C). The quantitative contribution (%) of reactive oxygen species (ROS) reveals that SO4•- are the dominating radical species, which contribute to ACN (58.3% for SO4•- radicals) and ACM degradation (46.4% for SO4•- radicals). The tafel plots and EIS spectra demonstrated that perovskites LaCoO3 have better charge transfer rates and more reactive sites that are favorable for PMS activation. Further, four major degradation pathways were proposed based on Fukui index calculations, as well as GC-MS characterization of intermediate byproducts. Based on a stability and reusability study, it was concluded that LaCoO3 perovskites are highly stable, and minimal cobalt leaching occurs (0.96 mg/L) after four cycles. The eco-toxicity assessment performed using QSAR model indicated that the byproducts of the LaCoO3/PMS system are non-toxic nature to common organism (i.e., fish, daphnids and green algae). In addition, the cost of the hybrid LaCoO3/PMS system in a single cycle was estimated to be $34.79 per cubic meter of resin wastewater.

Highly selective regulation of non-radical and radical mechanisms by Co cubic assembly catalysts for peroxymonosulfate activation.

Peroxymonosulfate (PMS) activation on efficient catalysts is a promising strategy to produce sulfate radical (SO4-) and singlet oxygen (1O2) for the degradation of refractory organic pollutants. It is a great challenge to selectively generate these two reactive oxygen species, and the regulation mechanism from non-radical to radical pathway and vice versa is not well established. Here, we report a strategy to regulate the activation mechanism of PMS for the selective generation of SO4- and 1O2 with 100 % efficiency by sulfur-doped cobalt cubic assembly catalysts that was derived from the Co-Co Prussian blue analog precursor. This catalyst showed superior catalytic performance in activating PMS with normalized reaction rate increased by 87 times that of the commercial Co3O4 nanoparticles and had much lower activation energy barrier for the degradation of organic pollutant (e.g., p-chlorophenol) (18.32 kJ⋅mol-1). Experimental and theoretical calculation results revealed that S doping can regulate the electronic structure of Co active centers, which alters the direction of electron transfer between catalyst and PMS. This catalyst showed a strong tolerance to common organic compounds and anions in water, wide environmental applicability, and performed well in different real-water systems. This study provides new opportunities for the development of metal catalyst with metal-organic frameworks structure and good self-regeneration ability geared specifically towards PMS-based advanced oxidation processes applied for water remediation.

Mediating peroxymonosulfate activation path in Fenton-like reaction via doping different metal atoms into g-C3N5.

Peroxymonosulfate (PMS) could be activated by either radical path or non-radical path, how to rationally mediate these two routines was an important unresolved issue. This work has introduced a simple way to address this problem via metal atom doping. It was found that Fe-doped nitrogen-rich graphitic carbon nitride (Fe-C3N5) exhibited high activity towards PMS activation for tetracycline degradation, and the degradation rate was 3.14 times higher than that of Co-doped nitrogen-rich graphitic carbon nitride (Co-C3N5). Radical trapping experiment revealed the contributions of reactive species over two catalysts were different. Electron paramagnetic resonance analysis further uncovered the non-radical activation path played a dominated role on Fe-C3N5 surface, while the radical activation path was the main routine on Co-C3N5 surface. Density functional theory calculations, X-ray photoelectron spectroscopy analysis, and electrochemical experiments provided convincing evidence to support these views. This study supplied a novel method to mediate PMS activation path via changing the doped metal atom in g-C3N5 skeleton, and it allowed us to better optimize the PMS activation efficiency.

Carboxymethyl chitosan modification of cobalt-zinc bimetallic MOF for tetracycline hydrochloride removal: Exploration of the enhancement mechanism of the process.

This study synthesized a carboxymethyl chitosan-modified bimetallic Co/Zn-ZIF (CZ@CMC) with strong hydrophilicity and adsorption performance via the one-pot method. Tetracycline hydrochloride (TCH) was used as the model contaminant to evaluate the adsorption and peroxymonosulfate (PMS) activation properties of CZ@CMC. Mechanism showed that the adsorption behavior occurred through pore filling, electrostatic attraction, surface complexation, hydrogen bonding, and π-π stacking. In addition, a CZ@CMC/PMS system was constructed, which had excellent catalytic performance. The hydrophilicity and selective adsorption properties of CMC conferred a greatly accelerated CZ@CMC in catalyzing the PMS process with kobs of 0.095 min-1, in which OH, 1O2, SO4-, O2-, and Co(III) were the main ROS which quenching tests, EPR, and chemical probe experiments verified. In addition, the degradation pathways of TCH were obtained utilizing DFT and HPLC-MS and analyzed to show that the system possessed a good detoxification capacity. This work is expected to provide a green, efficient, and stable strategy to enhance the adsorption properties of catalytic materials and subsequently their co-catalytic properties.

Encapsulating stable perovskite catalysts in hollow nanoreactors for enhanced pollutants degradation.

Creating a microenvironment for enhanced peroxymonosulfate (PMS) activation is vital in advanced oxidation processes. The objective of this study was to fabricate nanoshells composed of titanium dioxide embedded with cobalt titanate nanoparticles of perovskite to act as nanoreactors for effectively initiating PMS and degrading contaminants. The unique porous structure and confined space of the nanoreactor facilitated reactant absorption and mass transfer to the active sites, resulting in exceptional catalytic performance for pollutant elimination. Experimental findings revealed close to 100% decomposition efficiency of 4-chlorophenol (4-CP) within an hour utilizing the nanoreactors over a wide pH range. The TiO2/CoTiO3 hollow nanoshells catalysts also displayed adaptability in disintegrating organic dyes and antibiotics. The radicals SO4•-, •OH, and non-radicals 1O2 were determined to be accountable for eliminating pollutants, as supported by trapping experiments and electron paramagnetic resonance spectra. The catalyst was confirmed as an electron donor and PMS as an electron acceptor through electrochemical tests and density functional theory calculations. This study underscores the potential of incorporating stable perovskite catalysts in hollow nanoreactors to enhance wastewater treatment.

Porous-carbon/manganese composite catalyst transformed from waste biomass as peroxymonosulfate activator for carbamazepine degradation.

Activation of peroxymonosulfate (PMS) with solid catalysts for organic pharmaceutical degradation still faces challenge due to the demand of inexpensive catalysts. In this study, manganese-oxidizing microalgae (MOM) and its associated biogenic manganese oxides (BMO) were employed to prepare biomass-transformed porous-carbon/manganese (B-PC/Mn) catalyst through high-temperature calcination (850 °C). Remarkably, 100 % of carbamazepine (CBZ) was degraded within 30 min in the B-PC/Mn/PMS system. The degradation kinetic constant was 0.1718 min-1, which was 44.0 times higher than that of the biomass-transformed porous carbon mixed with MnOx activated PMS system. 1O2 was generated in the B-PC/Mn/PMS system, which is responsible for CBZ degradation. The MOM-BMO-associated structure greatly increased the specific surface areas and the contents of the C = O and pyrrolic-N groups, which facilitated PMS activation. The structure also induced the generation of Mn5C2, which exhibited a strong adsorption towards PMS. This study provides a novel strategy for preparing catalysts by using waste biomass.

Enhancing catalytic activity of CuCoFe-layered double oxide towards peroxymonosulfate activation by coupling with biochar derived from durian peel for antibiotic degradation: The role of C=O in biochar and underlying mechanism of built-in electric field.

CuCoFe-LDO/BCD was successfully synthesized from CuCoFe-LDH and biochar derived from durian shell (BCD). Ciprofloxacin (CFX) degraded more than 95% mainly by O2•- and 1O2 in CuCoFe-LDO/BCD(2/1)/PMS system within 10 min with a rate constant of 0.255 min-1, which was 14.35 and 2.66 times higher than those in BCD/PMS and CuCoFe-LDO/PMS systems, respectively. The catalytic system exhibited good performance over a wide pH range (3-9) and high degradation efficiency of other antibiotics. Built-in electric field (BIEF) driven by large difference in the work function/Fermi level ratio between CuCoFe-LDO and BCD accelerated continuous electron transfer from CuCoFe-LDO to BCD to result in two different microenvironments with opposite charges at the interface, which enhanced PMS adsorption and activation via different directions. As a non-radical, 1O2 was mainly generated via PMS activation by C=O in BCD. The presence of C=O in BCD resulted in an increase in atomic charge of C in C=O and redistributed the charge density of other C atoms. As a result, strong adsorption of PMS at C atom in C=O and other C with a high positive charge was favorable for 1O2 generation, whereas an enhanced adsorption of PMS at negatively charged C accounted for the generation of •OH and SO4•-. After adsorption, electrons in C of BCD became deficient and were fulfilled with those transferred from CuCoFe-LDO driven by BIEF, which ensured the high catalytic activity of CuCoFe-LDO/BCD. O2•-, on the other hand, was generated via several pathways that involved in the transformation of •OH and SO4•- originated from PMS activation by the transition of metal species in CuCoFe-LDO and negatively charged C in BCD. This study proposed a new idea of fabricating a low-cost metal-LDH and biomass-derived catalyst with a strong synergistic effect induced by BIEF for enhancing PMS activation and antibiotic degradation.

Inverted loading strategy regulates the Mn-OV-Ce sites for efficient fenton-like catalysis.

Regulating interfacial active sites to improve peroxymonosulfate (PMS) activation efficiency is a hot topic in the heterogeneous catalysis field. In this study, we develop an inverted loading strategy to engineer asymmetric Mn-OV-Ce sites for PMS activation. Mn3O4@CeO2 prepared by loading CeO2 nanoparticles onto Mn3O4 nanorods exhibits the highest catalytic activity and stability, which is due to the formation of more oxygen vacancies (OV) at the Mn-OV-Ce sites, and the surface CeO2 layer effectively inhibits corrosion by preventing the loss of manganese ion active species into the solution. In situ characterizations and density functional theory (DFT) studies have revealed effective bimetallic redox cycles at asymmetric Mn-OV-Ce active sites, which promote surface charge transfer, enhance the adsorption reaction activity of active species toward pollutants, and favor PMS activation to generate (•OH, SO4•-, O2•- and 1O2) active species. This study provides a brand-new perspective for engineering the interfacial behavior of PMS activation.

Effective activation of peroxymonosulfate by CoCr-LDH for removing organic contaminants in water: from lab-scale to practical applications.

In this study, CoCr layered double hydroxide material (CoCr-LDH) was prepared and used as an effective catalyst for peroxymonosulfate (PMS) activation to degrade organics in water. The prepared CoCr-LDH material had a crystalline structure and relatively porous structure, as determined by various surface analyses. In Rhodamine B (RhB) removal, the most outstanding PMS activation ability belongs to the material with a Co:Cr molar ratio of 2:1. The removal of RhB follows pseudo-first-order kinetics (R2 > 0.99) with an activation energy of 38.23 kJ/mol and efficiency of 98% after 7 min of treatment, and the total organic carbon of the solution reduced 47.2% after 10 min. The activation and oxidation mechanisms were proposed and the RhB degradation pathways were suggested with the key contribution of O2•- and 1O2. Notably, CoCr-LDH can activate PMS over a wide pH range of 4 - 9, and apply to a wide range of organic pollutants and aqueous environments. The material has high stability and good recovery, which can be reused for 5 cycles with a stable efficiency of above 88%, suggesting a high potential for practical recalcitrant water treatment via PMS activation by heterogeneous catalysts.

Insights into the efficient water treatment over N-doped carbon nanosheets with layered minerals as template: The role of interfacial electron tunneling and transfer.

Peroxymonosulfate (PMS) oxidation reactions have been extensively studied recently. Due to the high material cost and low catalytic capability, PMS oxidation technology cannot be effectively applied in an industrial water treatment process. In this work, we developed a modification strategy based on enhancing the neglected electron tunneling effect to optimize the intrinsic electron transport process of the catalyst. The 2D nitrogen-doped carbon-based nanosheets with small interlayer spacing were prepared by self-polymerization of dopamine hydrochloride inserted into the natural layered bentonite template. Systematic characterizations confirmed that the smaller layer spacing in the 2D nitride-doped carbon-based nanosheets reduces the depletion layer width. The weak electronic shielding effect derived by the small layer spacing on the material subsurface enhanced the bulk electron tunneling effect. More bulk electrons could be migrated to the catalyst surface to activate PMS molecules. The PMS activation system showed ultrafast oxidation capability to degrade organic pollutants and strong ability to resist interference from environmental matrixes due to the optimized electron transfer process. Furthermore, the developed membrane reactor exhibited strong catalytic stability during the continuous degradation of P-Chlorophenol (CP).

Co single atom coupled oxygen vacancy on W18O49 nanowires surface to construct asymmetric active site enhanced peroxymonosulfate activation.

Enhancing the activation of peroxymonosulfate (PMS) is essential for generating more reactive oxygen species in advanced oxidation process (AOPs). Nevertheless, improving PMS adsorption and expediting interfacial electron transfer to enhance reaction kinetics pose significant challenges. Herein, we construct confined W18O49 nanowires with asymmetric active centers containing Co-Vo-W (Vo: oxygen vacancy). The design incorporates surface-rich Vo and single-atom Co, and the resulting material is employed for PMS activation in water purification. By coupling unsaturated coordinated electrons in Vo with low-valence Co single atoms to construct an the "electron fountainhead", the adsorption and activation of PMS are enhanced. This results in the generation of more active free radicals (SO4•-, •OH, •O2-) and non-free radicals (1O2) for the decomposition of micropollutants. Thereinto, the degradation rate of bisphenol A (BPA) by Co-W18O49 is 32.6 times faster that of W18O49 monomer, which is also much higher than those of other transition-metal-doped W18O49 composites. This work is expected to help to elucidate the rational design and efficient PMS activation of catalysts with asymmetric active centers.

One-pot solvothermal synthesis of Cu-Fe-MOF for efficiently activating peroxymonosulfate to degrade organic pollutants in water:Effect of electron shuttle.

Persulfate-based advanced oxidation processes (PS-AOPs) show a bright prospect in sewage purification. The development of efficient catalysts with simple preparation process and eco-friendliness is the key for their applying in practical water treatment. Herein, a bimetallic Cu-Fe metal organic framework (MOF) was simply synthesized by using one-pot solvothermal methods and employed for activating peroxymonosulfate (PMS) to degrade organic pollutants in water. The Cu-Fe-MOF/PMS exhibited excellent degradation efficiencies (over 95% in 30 min) for a variety of pollutants, including phenol, bisphenol A, 2,4-dichlorophenol, methyl blue, rhodamine B, tetracycline and sulfamethoxazole. The degradation efficiency was impacted by dosages of Cu-Fe-MOF, PMS concentrations, reaction temperature, solution pH and anionic species. Phenol could be efficiently decomposed in a wide pH range of 5-9, with the highest degradation and mineralization efficiency of nearly 100% and 70%, respectively. Free radicals and non-free radicals participated in degrading of phenol at the same time, with dominantly free radical process, because sulfate radicals (SO4·-) and hydroxyl radicals (·OH) were the primary active substances by contribution calculation. Cu-Fe-MOF was acted as electron shuttle between molecules of phenol and PMS, and the cooperation effect of Fe and Cu on the Cu-Fe-MOF promoted the electron transfer, achieving the high degradation efficiency of phenol. Thus, Cu-Fe-MOF is an ideal catalyst for activating PMS, which is conducive to promote the applying of catalyst-activated PMS processes for practical wastewater treatments.

Role of tea polyphenols in enhancing the performance, sustainability, and catalytic cleaning capability of membrane separation for water-soluble pollutant removal.

Tea polyphenols (TPs), like green tea polyphenol (GTP) and black tea polyphenol (BTP), with phenolic hydroxyl structures, form coordination and hydrogen bonds, making them effective for bridging inorganic catalysts and membranes. Here, TPs were employed as interface agents for the preparation of TPs-modified needle-clustered NiCo-layered double hydroxide/graphene oxide membranes (NiCo-LDH-TPs/GO). The incorporation of porous guest material, NiCo-LDH-TPs, facilitated water channel expansion, enhancing membrane permeability and resulting in the development of high-performance, sustainable catalytic cleaning membranes. The introduction of TPs through coordination weakened the surface electronegativity of NiCo-LDH, promoting a uniform mixed dispersion with GO and facilitating membrane self-assembly. NiCo-LDH-GTP/GO-5 and NiCo-LDH-BTP/GO-5 membranes demonstrated permeances of 85.98 and 90.76 L m-2 h-1 bar-1, respectively, with rejections of 98.73% and 99.54% for methylene blue (MB). Notably, the NiCo-LDH-BTP/GO-5 membrane maintained a high rejection of 97.11% even after 18 cycles in the catalytic cleaning process. Furthermore, the modification of GTP and BTP enhanced MB degradation through PMS activation, resulting in a 0.33% and 0.35% increase in the reaction rate constants of NiCo-LDH, respectively, while reducing metal ion spillover. These findings highlighted the potential of TPs in enhancing the efficiency and sustainability of catalytic cleaning GO membranes for water purification and separation processes.