Application of novel magnetic lignin hydrogels: Activated persulfate degrades pesticide contaminants.

Lignin hydrogels have garnered significant attention due to their distinctive three-dimensional structures and potent swelling ability. In this work, a novel magnetic nanocomposite lignin hydrogel (MNLH) was fabricated through organic synthesis and solution immersion reduction. The obtained MNLH was used to activate persulfate(PDS) for pesticide degradation. Scanning electron microscopy (SEM), X-ray diffractometry (XRD), Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) were used to characterize the structure and morphology of MNLH. The influence of factors such as the lignin hydrogel to nano-zero-valent iron (nZVI) and copper oxide (CuO) mass ratio, MNLH dosage, initial pH on the MNLH/PDS/imidacloprid (IMI) system. Remarkably, the MNLH/PDS/IMI system has a removal rate of up to 100%. Quenching and electron paramagnetic resonance (EPR) studies disclosed that the MNLH/PDS system degraded IMI through a combination of free radical and non-free radical pathways, with the latter being dominant. More importantly, in this study, the toxicity and hydrolysis sites of IMI were analyzed using ECOSAR and Gaussian09, respectively, confirming the feasibility of activating persulfate with MNLH. These findings underscore the potential of MNLH as a function material suitable for facilitating the persulfate-activated degradation of organic pollutants.

Biochar Meets Single-Atom: A Catalyst for Efficient Utilization in Environmental Protection Applications and Energy Conversion.

Single-atom catalysts (SACs), combining the advantages of multiphase and homogeneous catalysis, have been increasingly investigated in various catalytic applications. Carbon-based SACs have attracted much attention due to their large specific surface area, high porosity, particular electronic structure, and excellent stability. As a cheap and readily available carbon material, biochar has begun to be used as an alternative to carbon nanotubes, graphene, and other such expensive carbon matrices to prepare SACs. However, a review of biochar-based SACs for environmental pollutant removal and energy conversion and storage is lacking. This review focuses on strategies for synthesizing biochar-based SACs, such as pre-treatment of organisms with metal salts, insertion of metal elements into biochar, or pyrolysis of metal-rich biomass, which are more simplistic ways of synthesizing SACs. Meanwhile, this paper attempts to 1) demonstrate their applications in environmental remediation based on advanced oxidation technology and energy conversion and storage based on electrocatalysis; 2) reveal the catalytic oxidation mechanism in different catalytic systems; 3) discuss the stability of biochar-based SACs; and 4) present the future developments and challenges regarding biochar-based SACs.

Hydrogen Bonds and In-situ Photoinduced Metallic Bi0/Ni0 Accelerating Z-scheme Charge Transfer of BiOBr@NiFe-LDH for Highly Efficient Photocatalysis.

For heterojunction system, the lack of stable interfacial driving force and definite charge transfer channel makes the charge separation and transfer efficiency unsatisfactory. The photoreaction mechanism occurring at the interface also receives less attention. Herein, a 2D/2D Z-scheme junction BiOBr@NiFe-LDH with large-area contact featured by abundant interfacial hydrogen bonds and a strong interfacial electric field (IEF) is synthesized, and in-situ photoinduced metallic species assisting charge transfer mechanism is demonstrated. The hydrogen bonds between O atoms from BiOBr and H atoms from NiFe-LDH induce a significant interfacial charge redistribution, establishing a robust IEF. Notably, during photocatalytic reaction, Bi0 and Ni0 are in-situ isolated from BiOBr and NiFe-LDH in heterojunction, which separately act as electron transport mediator and electron trap to further accelerate charge transfer efficiency up to 71.2%. Theoretical calculations further demonstrate that the existence of Bi0 strengthens the IEF. Therefore, high-speed spatial charge separation is realized in Bi0/BiOBr@Ni0/NiFe-LDH, leading to a prominent photocatalytic activity with a tetracycline removal ratio of 88.3% within 7 minutes under visible-light irradiation and the presence of persulfate, far exceeding majority of photocatalysts reported previously. This study provides valid insights for designing hydrogen bonding heterojunction systems, and advances mechanistic understanding on in-situ photoreaction at interfaces.

Synthesis of copper/carbon nanofibers by electrostatic spinning toward persulfate activation for treatment of antibiotic wastewater.

Antibiotics in water will cause serious harm to human health and ecosystem. Carbon-based materials and transition metals activated peroxodisulfate (PDS) to produce active species, which can degrade residual antibiotics in water. In this paper, Cu/CNF (carbon nanofibers) composites were first prepared by introducing Cu into CNF using electrostatic spinning technology, which was used to activate PDS to degrade tetracycline (TC). The degradation efficiency of Cu/CNF/PDS was 36.23% higher than that of CNF/PDS. The reason is that introducing Cu can increase the number of surface functional groups and specific surface area of CNF, and then improve the catalytic performance. The functional groups and Cu species are the active sites for catalytic PDS. Moreover, the main ways to degrade TC in the Cu/CNF/PDS system are singlet oxygen (1O2) and electron transfer. Based on the above analysis, we modified CNF with transition metal salts, prepared efficient environmental functional materials, and used them for PDS activation, providing a theoretical basis and technical support for the degradation of antibiotic pollutants and creating new ideas for other research.

Mechanistic insights into δ-MnO2/biochar-activated persulfate-treated wastewater containing antibiotics and heavy metals: Nonradical pathway and pivotal role of Cu(⠡) at low temperature.

Herein, we present a high efficiency system based on biochar loaded with layered manganese dioxide to remove tetracycline and heavy metals from livestock wastewater. Under the optimal conditions, the degradation efficiencies of TC in the δ-MnO2/BC/PS system were 85.5% at 25 °C and 38.5% at 5 °C. Radical quenching experiments revealed that radical reactions in the δ-MnO2/BC/PS system were weak under 15 °C. Adsorption degradation experiments showed that the system maintained good adsorption performance at 5 °C. Galvanic cell experiments and cyclic voltammetry showed that the δ-MnO2/BC material had good electrochemical activity and high stability in response to temperature, indicating that TC was degraded by a nonradical pathway that was not limited by temperature, such as electron transfer. Copper ion was important coadsorbent and coactivator of the reaction system. Furthermore, FTIR, XPS, and X-ray diffraction (XRD) analyses showed that Cu(II) in the system was involved in changing the manganese valence state in the δ-MnO2/BC material and increasing the -OH content of BC. Comparison of the different products generated during metabolic testing revealed that the reaction pathway of the system at low temperature (5 °C) differed from that at normal temperature (25 °C). The δ-MnO2/BC material demonstrated good removal ability for antibiotics and heavy metals at normal and low temperatures in actual biogas slurry. The study provides insight for improving the efficiency of environmentally friendly treatments of aquaculture wastewater in cold regions, which is of great significance for resource utilization.

A critical review of persulfate-based electrochemical advanced oxidation processes for the degradation of emerging contaminants: From mechanisms and electrode materials to applications.

The persulfate-based electrochemical advanced oxidation processes (PS-EAOPs) exhibit distinctive advantages in the degradation of emerging contaminants (ECs) and have garnered significant attention among researchers, leading to a consistent surge in related research publications over the past decade. Regrettably, there is still a lack of a critical review gaining deep into understanding of ECs degradation by PS-EAOPs. To address the knowledge gaps, in this review, the mechanism of electro-activated PS at the interface of the electrodes (anode, cathode and particle electrodes) is elaborated. The correlation between these electrode materials and the activation mechanism of PS is systematically discussed. The strategies for improving the performance of electrode material that determining the efficiency of PS-EAOPs are also summarized. Then, the applications of PS-EAOPs for the degradation of ECs are described. Finally, the challenges and outlook of PS-EAOPs are discussed. In summary, this review offers valuable guidance for the degradation of ECs by PS-EAOPs.

Knowledge graph and development hotspots of biochar as an emerging aquatic antibiotic remediator: A scientometric exploration based on VOSviewer and CiteSpace.

As an emerging material in the field of environmental remediation, biochar produced by carbonisation of organic solid waste has been widely used in the remediation of antibiotic wastewater due to its environmental friendliness and excellent adsorption properties. This study analyses the current literature in the field in a comprehensive and scientific manner using CiteSpace and VOSviewer technologies. Between 2011 and 2023, a total of 1162 papers were published in this domain, spanning three distinct stages: applied methods, mechanism investigation, and enhanced improvement. The results of keyword clustering indicate that the remediation of antibiotics complexed with multiple pollutants by biochar is the main research topic, followed by the remediation of antibiotics by biochar in combination with other technologies. Furthermore, drawing from current research hotspots in antibiotic remediation using biochar, this study identified the pivotal mechanisms involved: (1) The primary mechanisms by which raw biochar remediates antibiotics include π-π electron donor-acceptor interactions, hydrophobic interactions, electrostatic interactions, hydrogen-bonding, and pore filling. (2) Steam activation, acid/base, metal salt/metal oxide, and clay mineral modification can improve the physical/chemical properties of biochar, enhancing its adsorptive removal of antibiotics. (3) Biochar activated persulfate and degraded antibiotics via free radical pathways (SO4-•, •OH and O2-•) as well as non-free radical pathways (1O2 and electron transfer). In addition, the challenge and prospect of biochar engineering applications for antibiotic remediation lies in improving the main mechanism of antibiotic remediation by biochar. The prospective utilization of biochar in enhancing the remediation of antibiotic-related pollutants holds tremendous value for the future.

Green mechanochemical activation of solid persulfate to remove PAHs in soil: Performance and mechanism.

Due to the high biotoxicity and persistence of polycyclic aromatic hydrocarbons (PAHs), the remediation of PAHs-contaminated soil becomes an intractable problem. Persulfate-based advanced oxidation processes are widely used to degrade PAHs in aquatic environment. However, they are not convenient for used in soil due to the heterogeneity and complexity of soil matrix. In this study, a green and convenient ball milling process is introduced to activate persulfate for the remediation of PAHs-contaminated soil. About 82.5% PAHs were removed with 10% wt. Na2S2O8 (PS) addition and ball-milling for 2 h under 500 r/min. The degradation of PAHs is attributed to the attack of radicals (SO4·- and·OH) generated from the activation of PS by mechanochemistry. Moreover, stable Si-O bonds were disrupted during ball-milling process, and formed free electron on the surface of soil particles. This facilitates the electron transfer from oxidants to contaminants. The particle size, surface element composition, functional group, and thermogravimetric analysis confirmed the slight disturbance of ball-milling-assisted PS process on the physical and chemical properties of soil. Therefore, ball-milling assisted PS approach would be a promising technology for the remediation of PAHs-contaminated soil.

Dual Z-scheme heterojunction Ce2Sn2O7/Ag3PO4/V@g-C3N4 for increased photocatalytic degradation of the food additive tartrazine, in the presence of persulfate: Kinetics, toxicity, and density functional theory studies.

This study involved the synthesis of a Ce2Sn2O7/Ag3PO4/V@g-C3N4 composite through hydrothermal methods, followed by mechanical grinding. The resulting heterojunction exhibited improved catalytic activity under visible light by effectively separating electrons and holes (e-/h+). The degradation of Tartrazine (TTZ) reached 93.20% within 50 min by employing a ternary composite at a concentration of 10 mg L-1, along with 6 mg L-1 of PS. The highest pseudo-first-order kinetic constant (0.1273 min-1 and R2 = 0.951) was observed in this system. The dual Z-scheme heterojunction is developed by Ce2Sn2O7, Ag3PO4, and V@g-C3N4, and it may increase the visible light absorption range while also accelerating charge carrier transfer and separation between catalysts. The analysis of the vulnerability positions and degradation pathways of TTZ involved the utilization of density functional theory (DFT) and gas chromatography-mass spectrometry (GC-MS) to examine the intermediate products. Therefore, Ce2Sn2O7/Ag3PO4/V@g-C3N4 is an excellent ternary nanocomposite for the remediation of pollutants.

Chemical inertness conversion of carbon fraction in coal gangue via N-doping for efficient benzo(a)pyrene degradation.

Efficient degradation of organic pollutants in complex media via advanced oxidation processes (AOPs) is still critical and challenging. Herein, nitrogen (N)-doped coal gangue (CG) catalysts (N-CG) with economic competitiveness and environmental friendliness were successfully synthesized to activate peroxymonosulfate (PMS), exhibiting ultrafast degradation performance toward benzo(a)pyrene (BaP) with 100.00 % and 93.21 % in contaminated solution and soil under optimized condition, respectively. In addition, 0.4 N-CG possessed excellent reusability toward BaP degradation with over 80.00 % after five cycles. However, BaP removal efficiency was significantly affected by some co-existing anions (HCO3- and SO42-) and humic acid (HA) in solution and soil, as well as inhibited under alkaline conditions, especially pH ≥ 9. According to the characterizations, N-doping could promote the generation of pyridinic N and graphitic N in N-CG via high-temperature calcination, which was conducive to produce hydroxyl radical (•OH), sulfate radical (SO4•-), superoxide radical (•O2-) and single oxygen (1O2). In 0.4 N-CG/PMS system, 1O2 and •O2- were proved to be the predominant reactive oxygen species (ROSs) in BaP degradation, as well as •OH and SO4•- made certain contributions. To sum up, this work provided a promising strategy for synthesis of CG-based catalysts by chemical inertness conversion of carbon fracture via N-doping for PMS activation and opened a novel perspective for environmental remediation of hydrophobic and hydrophilic contaminants pollution.

The CoO-doped carbon nanotubes enhance electronic performance and effectively activate persulfate for the degradation of sulfafurazole.

In recent studies, carbon nanotube (CNTs) materials and their composites have demonstrated remarkable catalytic activity in the activation of persulfate (PS), facilitating the efficient degradation of organic pollutants. In this study, a novel Co loaded carbon nanotubes (CoO@CNT) catalyst was prepared to promote PDS activation for the degradation of sulfafurazole (SIZ). Experimental results, the CNT as a carrier effectively reduces the leaching of cobalt ions and improves the electron transport capacity，whereas the introduced Co effectively activates the PDS, promoting the generation of highly reactive radicals to degrade SIZ. Under optimized conditions (a catalyst dose of 0.2 g/L, a PDS dose of 1 g/L and an initial pH = 9.0), the obtained CoO@CNT demonstrated favorable Fenton-like performance, reaching a degradation efficiency of 95.55% within 30 min. Furthermore, density functional theory (DFT) calculations demonstrate that the introduction of cobalt (Co) accelerates electron transfer, promoting the decomposition of PDS while facilitating the Co2+/Co3+ redox cycling. We further employed the environmental chemistry and risk assessment system (ECOSAR) to evaluate the ecological toxicity of intermediate products, revealing a significant reduction in ecological toxicity associated with this degradation process, thereby confirming its environmental harmlessness. Through batch experiments and studies, we gained a comprehensive understanding of the mechanism and influencing factors of CoO@CNT in the role of SIZ degradation, and provided robust support for evaluating the ecological toxicity of degradation products. This study provides a significant strategy for the development of efficient catalysts incorporating Co for the environmentally friendly degradation of organic pollutants.

Effective degradation of synthetic micropollutants and real textile wastewater via a visible light-activated persulfate system using novel spinach leaf-derived biochar.

A novel biochar (BC), derived from spinach leaves, was utilized as an activator for persulfate (PS) in the degradation of methylene blue (MB) dye under visible light conditions. Thorough analyses were conducted to characterize the physical and chemical properties of the biochar. The (BC + light)/PS system exhibited superior MB degradation efficiency at 83.36%, surpassing the performance of (BC + light)/hydrogen peroxide and (BC + light)/peroxymonosulfate systems. The optimal conditions were ascertained through the implementation of response surface methodology. Moreover, the (BC + light)/PS system demonstrated notable degradation ratios of 90.82%, 81.88%, and 84.82% for bromothymol blue dye, paracetamol, and chlorpyrifos, respectively, under optimal conditions. The predominant reactive species responsible for MB degradation were identified as sulfate radicals. Notably, the proposed system consistently achieved high removal efficiencies of 99.02%, 96.97%, 94.94%, 92%, and 90.35% for MB in five consecutive runs. The applicability of the suggested system was further validated through its effectiveness in treating real textile wastewater, exhibiting a substantial MB removal efficiency of 98.31% and dissolved organic carbon mineralization of 87.49%.

MXene-supported MIL-88A(Fe) as persulfate activator for removal of tetracycline.

The poor conductivity, poor stability, and agglomeration of iron-based metal organic framework MIL-88A(Fe) limit its application as persulfate (PS) activator in water purification. Herein, MXene-supported MIL-88A(Fe) composites (M88A/MX) were synthesized to enhance its adsorption and catalytic capability for tetracycline (TC) removal. Scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR), and X-ray photoelectron spectroscopy (XPS) were used to characterize prepared materials, confirming the successful attachment of MIL-88A(Fe) to the surface of MXene. M88A/MX-0.2 composites, prepared with 0.2 g MXene addition, exhibit optimal degradation efficiency, reaching 98% under conditions of 0.2 g/L M88A/MX-0.2, 1.0 mM PS, 20 ppm TC, and pH 5. The degradation rate constants of M88A/MX-0.2 were 0.03217 min-1, which was much higher than that of MIL-88A(Fe) (0.00159 min-1) and MXene (0.00626 min-1). The removal effects of reaction parameters, such as dosage of M88A/MX-0.2 and PS; initial solution pH; and the presence of the common co-existing constituents (humic acid and the inorganic anions) were investigated in detail. Additionally, the reuse of M88A/MX-0.2 showed that the composites had good cycling stability by recurrent experiments. The results of electron paramagnetic resonance (EPR) and quenching experiments indicated that ·OH, ·SO4-, and ·O2- were involved in the M88A/MX-0.2/PS system where persulfate oxidation process was activated with prepared M88A/MX-0.2. In addition, the intermediates of photocatalytic degradation were determined by HPLC-MS, and the possible degradation pathways of the target molecules were inferred. This study offered a new avenue for sulfate-based degradation of Fe-based metal organic framework.

Remediation of polycyclic aromatic hydrocarbons polluted soil by biochar loaded humic acid activating persulfate: performance, process and mechanisms.

The remediation for polycyclic aromatic hydrocarbons contaminated soil with cost-effective method has received significant public concern, a composite material, therefore, been fabricated by loading humic acid into biochar in this study to activate persulfate for naphthalene, pyrene and benzo(a)pyrene remediation. Experimental results proved the hypothesis that biochar loaded humic acid combined both advantages of individual materials in polycyclic aromatic hydrocarbons adsorption and persulfate activation, achieved synergistic performance in naphthalene, pyrene and benzo(a)pyrene removal from aqueous solution with efficiency reached at 98.2%, 99.3% and 90.1%, respectively. In addition, degradation played a crucial role in polycyclic aromatic hydrocarbons remediation, converting polycyclic aromatic hydrocarbons into less toxic intermediates through radicals of ·SO4-, ·OH, ·O2-, and 1O2 generated from persulfate activation process. Despite pH fluctuation and interfering ions inhibited remediation efficiency in some extent, the excellent performances of composite material in two field soil samples (76.7% and 91.9%) highlighted its potential in large-scale remediation.

Sulfur-containing iron carbon nanocomposites activate persulfate for combined chemical oxidation and microbial remediation of petroleum-polluted soil.

In this study, sulfur-containing iron carbon nanocomposites (S@Fe-CN) were synthesized by calcining iron-loaded biomass and utilized to activate persulfate (PS) for the combined chemical oxidation and microbial remediation of petroleum-polluted soil. The highest removal efficiency of total petroleum hydrocarbons (TPHs) was achieved at 0.2% of activator, 1% of PS and 1:1 soil-water ratio. The EPR and quenching experiments demonstrated that the degradation of TPHs was caused by the combination of 1O2,·OH, SO4·-, and O2·-. In the S@Fe-CN activated PS (S@Fe-CN/PS) system, the degradation of TPHs underwent two phases: chemical oxidation (days 0 to 3) and microbial degradation (days 3 to 28), with kinetic constants consistent with the pseudo-first-order kinetics of chemical and microbial remediation, respectively. In the S@Fe-CN/PS system, soil enzyme activities decreased and then increased, indicating that microbial activities were restored after chemical oxidation under the protection of the activators. The microbial community analysis showed that the S@Fe-CN/PS group affected the abundance and structure of microorganisms, with the relative abundance of TPH-degrading bacteria increased after 28 days. Moreover, S@Fe-CN/PS enhanced the microbial interactions and mitigated microbial competition, thereby improving the ability of indigenous microorganisms to degrade TPHs.

Ce/N @BC prepared based on plant metallurgy strategy: A novel activator of peroxymonosulfate for the degradation of sulfamethoxazole.

A novel carbon catalyst was created based on plant metallurgy strategy for organic pollutants removal. Plants rich in CeO2 NPs in water were used as carbon precursors and pyrolyzed with urea to obtain Ce/N co-doped carbon catalysts, which were used in the degradation of sulfamethoxazole (SMX) by active peroxymonosulfate (PMS). The results showed that the Ce/N @BC/PMS system achieved to 94.5% degradation of SMX in 40 min at a rate constant of 0.0602 cm-1. The activation center of PMS is widely dispersed Ce oxide nanocrystals, and CeO2 NPs promote the formation of oxygen centered PFR with enhanced catalytic ability and longer half-life. In addition, N-doping facilitates the transfer of π-electrons within the sp2 carbon of biochar, increasing active sites and thus improving PMS activation efficiency. The degradation process was contributed to by both radical and non-radical activation mechanisms including 1O2 and direct electron transfer, with O2•- serving as 1O2's precursor. Through the DFT calculations, LC-MS and toxicological analyses, the degradation pathway of pollutants and the toxicity changes throughout the entire degradation process were further revealed, indicating that the degradation of SMX could effectively reduce ecological toxicity.

Degradation of triclosan by peroxydisulfate/peroxomonosulfate binary oxidants activation under thermal conditions: Efficiency and mechanism.

Peroxydisulfate (PDS) and peroxymonosulfate (PMS) could be efficiently activated by heat to generate reactive oxygen species (ROS) for the degradation of organic contaminants. However, defects including the inefficiency treatment and pH dependence of monooxidant process are prominent. In this study, synergy of heat and the PDS-PMS binary oxidant was studied for efficient triclosan (TCS) degradation and apply in rubber wastewater. Under different pH values, the degradation of TCS followed pseudo-first-order kinetics, the reaction rate constant (kobs) value of TCS in heat/PDS/PMS system increased from 1.8 to 4.4 fold and 6.8-49.1 fold when compared to heat/PDS system and heat/PMS system, respectively. Hydroxyl radicals (·OH), sulfate radicals (SO4·-) and singlet oxygen (1O2) were the major ROS for the degradation of TCS in heat/PDS/PMS system. In addition, the steady-state concentrations of ·OH/1O2 and SO4·-/·OH/1O2 increased under acidic conditions and alkaline conditions, respectively. It was concluded that the pH regulated the ROS for degradation of TCS in heat/PDS/PMS system significantly. Based on the analysis of degradation byproducts, it was inferred that the dechlorination, hydroxylation and ether bond breaking reactions occurred during the degradation of TCS. Moreover, the biological toxicity of the ten byproducts was lower than that of TCS was determined. Furthermore, the heat/PDS/PMS system is resistant to the influence of water substrates and can effectively improve the water quality of rubber wastewater. This study provides a novel perspective for efficient degradation of TCS independent of pH in the heat/PDS/PMS system and its application of rubber wastewater.

Effective degradation of tetracycline and real pharmaceutical wastewater using novel nanocomposites of biosynthesized ZnO and carbonized toner powder.

In this study, novel nanohybrids of biosynthesized zinc oxide (ZnO) and magnetite-nanocarbon (Fe3O4-NC) obtained from the carbonization of toner powder waste were fabricated and investigated for persulfate (PS) activation for the efficient degradation of tetracycline (TCN). The chemical and physical properties of the synthesized catalysts were analyzed using advanced techniques. ZnO/Fe3O4-NC nanohybrid with mass ratio 1:2, respectively in the presence of PS showed the highest TCN removal efficiency compared to the individual components (ZnO and Fe3O4-NC) and other nanohybrids with mass ratios of 1:1 and 2:1. The results indicated that efficient degradation of TCN could be attained at pH 3-7. The optimum operating parameters were TCN concentration of 12.8 mg/L, PS concentration of 7 Mm, and catalyst dose of 0.55 g/L. The high stability of ZnO/Fe3O4-NC (1:2) nanocomposite was assured by the slight drop in TCN degradation percentage from 97.27% to 85.45% after five successive runs under the optimum conditions and the concentrations of leached iron and zinc into the solution were monitored. The quenching experiments explored that the prevailing reactive entities were sulfate radicals. Additionally, the degradation of TCN in various water matrices was investigated, and a degradation pathway was suggested. Further, degradation of real pharmaceutical waste was conducted showing that the removal efficiencies of TCN, total organic carbon (TOC), and chemical oxygen demand (COD) were 89.79, 80.65, and 78.64% after 2 h under the optimum conditions. The effectiveness of the proposed system (ZnO/Fe3O4-NC (1:2) @ PS) for the degradation of real samples compiled from industrial effluents as well as its inexpensiveness and green nature qualify this system for the full-scale application.

Heteroatom substitution enhances generation and reactivity of surface-activated peroxydisulfate complexes for catalytic fenton-like reactions.

Peroxydisulfate (PDS)-based Fenton-like reactions are promising advanced oxidation processes (AOPs) to degrade recalcitrant organic water pollutants. Current research predominantly focuses on augmenting the generation of reactive species (e.g., surface-activated PDS complexes (PDS*) to improve treatment efficiency, but overlooks the potential benefits of enhancing the reactivity of these species. Here, we enhanced PDS* generation and reactivity by incorporating Zn into CuO catalyst lattice, which resulted in 99% degradation of 4-chlorophenol within only 10 min. Zn increased PDS* generation by nearly doubling PDS adsorption while maintaining similar PDS to PDS* conversion efficiency, and induced higher PDS* reactivity than the common catalyst CuO, as indicated by a 4.1-fold larger slope between adsorbed PDS and open circuit potential of a catalytic electrode. Cu-O-Zn formation upshifts the d-band center of Cu sites and lowers the energy barrier for PDS adsorption and sulfate desorption, resulting in enhanced PDS* generation and reactivity. Overall, this study informs strategies to enhance PDS* reactivity and design highly active catalysts for efficient AOPs.

Efficient benzo(a)pyrene degradation by coal gangue-based catalytic material for peroxymonosulfate activation.

A low cost and green peroxymonosulfate (PMS) activation catalyst (CG-Ca-N) was successfully prepared with coal gangue (CG), calcium chloride, and melamine as activator. Under the optimal conditions, the CG-Ca-N can remove 100 % for benzo(a)pyrene (Bap) in an aqueous solution after 20 min and 72.06 % in soil slurry medium within 60 min, which also display excellent reuse ability toward Bap after three times. The removal of Bap is significantly decreased when the initial pH value was greater than 9 and obviously inhibited in the presence of HCO3- or SO42-. The characterization results indicated that the addition of calcium chloride could stabilize and increase the content of pyridinic N during thermal annealing, resulting in the production of •OH, SO4•- and 1O2. Based on electron paramagnetic resonance (EPR) and active radical scavenging experiments, 1O2 could be identified to be the dominant role in Bap degradation. Overall, this work opened a new perspective for the low cost and green PMS catalysts and offered great promise in the practical remediation of organic pollution of groundwater and soil.