Electrical breakdown in liquid-phase processing on an enhancement of 7-hydroxymitragynine conversion from mitragynine in Mitragyna speciose (Kratom).

This study investigates the impact of the Electrical Breakdown in Liquid-phase (EBL) process on alkaloid transformation in Mitragyna speciose (Kratom) leaves, focusing on the conversion of mitragynine (MG) to 7-hydroxy mitragynine (7-OH-MG) by using advanced oxidation processes (AOPs). A novel reactor has been developed to enhance plasma exposure to Kratom leaf powdered solutions during the EBL process. Two distinct electrical voltage characteristics, half-positive and negative half-waves, have been utilized for the EBL, with an output voltage of 4.57 kVpeak at a no-load condition and a frequency of 50 Hz. The experimental findings demonstrate a time-dependent enhancement in the transformation process. The highest yield of 7-OH-MG, reaching 2,485 ± 134 µg/g of dried Kratom leaves weight, has been attained with the EBL processing generated by positive half-wave voltage after 20 min of EBL exposure. Notably, the EBL processing generated by positive half-wave voltage has outperformed the one generated by negative half-wave voltage by a significant factor of 2.01.

Singlet oxygen dominant-activation by hollow structural cobalt-based MOF/peroxymonosulfate system for micropollutant removal.

Despite the keen interest in potentially using the metal-organic framework (MOF) in advanced oxidation processes (AOPs), their application for environmental abatement and the corresponding degradation mechanisms have remained largely elusive. This study explores the use of cobalt-based MOF (CoMOF) for peroxymonosulfate (PMS) activation to remove tetracycline (TC) from water resources. Under optimal conditions, the given catalytic system could achieve a TC removal of 83.3%. Radical quenching tests and EPR analysis revealed that SO4•-, HO•, •O2-, and 1O2 could participate in the catalytic degradation, but the discernible removal mechanism was mainly ascribed to the nonradical pathway induced by 1O2. At only 5 mg/L of CoMOF, the performance of the catalytic system was superior to that of PMS alone for different types of micropollutants. The CoMOF/PMS system could also reliably deal with typical anions in water, such as Cl-, SO42-, HCO3-, and PO43-. The MOF catalyst could last for four cycles with a minor decrease in reactivity of ∼30%. However, the removal performance decreased markedly when aromatic natural organic matter (NOM) were present in the water bodies, and the effectiveness was lower in alkaline or acidic environments. Our work offers insights into the catalytic degradation of CoMOF/PMS applied in contaminated water remediation and serves as a baseline for fabricating an efficient MOF with enhanced catalytic performance and stability.

Recent advances in the removal of psychoactive substances from aquatic environments: A review.

Psychoactive substances (PS) have become emerging contaminants in aquatic environments, characterized by their wide distribution, high persistence, bioaccumulation and toxicity. They are difficult to be completely removed in sewage treatment plants due to their high stability under different conditions. The incomplete removal of PS poses a threat to the aquatic animals and can also lead to human health problems through accumulation in the food chain. PS has become a huge burden on global health systems. Therefore, finding an effective technology to completely remove PS has become a "hot topic" for researchers. The methods for removal PS include physical techniques, chemical methods and biological approaches. However, there is still a lack of comprehensive and systematic exploration of these methods. This review aims to address this gap by providing a comprehensive overview of traditional strategies, highlighting recent advancements, and emphasizing the potential of natural aquatic plants in removing trace PS from water environments. Additionally, the degradation mechanisms that occur during the treatment process were discussed and an evaluation of the strengths and weaknesses associated with each method was provided. This work would help researchers in gaining a deeper understanding of the methodologies employed and serve as a reference point for future research endeavors and promoting the sustainable and large-scale application of PS elimination.

Nitrogen and magnesium codoped biochar activates periodate to remediate bensulfuron methyl-contaminated water at low temperature: Performance, mechanisms, and phytotoxicity.

Bensulfuron methyl (BSM), a typical sulfonylurea herbicide, has been widely used worldwide for weed suppression and crop protection. Nevertheless, the long-term and prolonged usage led to residues in environment, resulting in the reduction of crop yields and even threatening food security. In this study, the nitrogen/magnesium codoped biochar (NMg-BC) was prepared via two-step pyrolysis method to activate periodate (PI) for BSM degradation. The results demonstrated BSM degradation rate was 87.9 % within 10 min by NMg-BC/PI system at 15 â„ƒ. The system exhibited the favorable tolerance to environmental changes (pH, temperature, anions, and humic acids), presenting high removal efficiency of BSM. Radicals (IO3•) and non-radicals (1O2 and electron transfer) pathways contributed to the degradation of BSM, while the latter performed a crucial role in BSM degradation. Theoretical calculations further confirmed doped of N and Mg changed the electron configuration and electrostatic potential (ESP) distribution of biochar, which was beneficial to provide more active sites for PI activation. Hydroponic experiments showed that NMg-BC/PI system could effectively degrade BSM, and its residue had no significant effect on the length and weight of soybean. The study provides a promising approach for the pollutant remediation in cold regions.

Marine toxins in environment: Recent updates on depuration techniques.

Marine toxins pose a significant safety risk, leading to human intoxications and causing substantial economic losses in seafood-producing regions. The development of rapid, cost-effective, efficient, and reliable approaches for the containment of these substances is therefore crucial in order to mitigate the adverse impact of marine toxins. This research conducted a comprehensive review on the toxicity and influencing factors of marine toxins production. Additionally, depuration technologies, including adsorption, advanced oxidation processes, biodegradation, heating treatment, temporary maintenance and purification, and drug inhibition, were systematically summarized. The study also provided a comparative analysis of the advantages and disadvantages of various depuration technologies and proposed strategies for future development.

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.

A critical review of ozone-based electrochemical advanced oxidation processes for water treatment: Fundamentals, stability evaluation, and application.

In recent years, electrochemical advanced oxidation processes (EAOPs) combined with ozonation have been widely utilized in water/wastewater treatment due to their excellent synergistic effect, high treatment efficiency, and low energy consumption. A comprehensive summary of these ozone-based EAOPs is still insufficient, though some reviews have covered these topics but either focused on a specific integrated process or provided synopses of EAOPs or ozone-based AOPs. This review presents an overview of the fundamentals of several ozone-based EAOPs, focusing on process optimization, electrode selection, and typical reactor designs. Additionally, the service life of electrodes and improvement strategies for the stability of ozone-based EAOPs that are ignored by previous reviews are discussed. Furthermore, four main application fields are summarized, including disinfection, emerging contaminants treatment, industrial wastewater treatment, and resource recovery. Finally, the summary and perspective on ozone-based EAOPs are proposed. This review provides an overall summary that would help to gain insight into the ozone-based EAOPs to improve their environmental applications.

Rapid and Highly Selective Fe(IV) Generation by Fe(II)-Peroxyacid Advanced Oxidation Processes: Mechanistic Investigation via Kinetics and Density Functional Theory.

High-valent iron (Fe(IV/V/VI)) has been widely applied in water decontamination. However, common Fe(II)-activating oxidants including hydrogen peroxide (H2O2) and persulfate react slowly with Fe(II) and exhibit low selectivity for Fe(IV) production due to the cogeneration of radicals. Herein, we report peroxyacids (POAs; R-C(O)OOH) that can react with Fe(II) more than 3 orders of magnitude faster than H2O2, with high selectivity for Fe(IV) generation. Rapid degradation of bisphenol A (BPA, an endocrine disruptor) was achieved by the combination of Fe(II) with performic acid (PFA), peracetic acid (PAA), or perpropionic acid (PPA) within one second. Experiments with phenyl methyl sulfoxide (PMSO) and tert-butyl alcohol (TBA) revealed Fe(IV) as the major reactive species in all three Fe(II)-POA systems, with a minor contribution of radicals (i.e., •OH and R-C(O)O•). To understand the exceptionally high reactivity of POAs, a detailed computational comparison among the Fenton-like reactions with step-by-step thermodynamic evaluation was conducted. The high reactivity is attributed to the lower energy barriers for O-O bond cleavage, which is determined as the rate-limiting step for the Fenton-like reactions, and the thermodynamically favorable bidentate binding pathway of POA with iron. Overall, this study advances knowledge on POAs as novel Fenton-like reagents and sheds light on computational chemistry for these systems.

Selective O2-to-H2O2 Electrosynthesis by a High-Performance, Single-Pass Electrofiltration System Using Ibuprofen-Laden CNT Membranes.

Producing H2O2 through a selective, two-electron (2e) oxygen reduction reaction (ORR) is challenging, especially when it serves as an advanced oxidation process (AOP) for cost-effective water decontamination. Herein, we attain a 2e-selectivity H2O2 production using a carbon nanotube electrified membrane with ibuprofen (IBU) molecules laden (IBU@CNT-EM) in an ultrafast, single-pass electrofiltration process. The IBU@CNT-EM can generate H2O2 at a rate of 25.62 mol gCNT-1 h-1 L-1 in the permeate with a residence time of 1.81 s. We demonstrated that an interwoven, hydrophilic-hydrophobic membrane nanostructure offers an excellent air-to-water transport platform for ORR acceleration. The electron transfer number of the ORR for IBU@CNT at neutral pH was confirmed as 2.71, elucidating a near-2e selectivity to H2O2. Density functional theory (DFT) studies validated an exceptional charge distribution of the IBU@CNT for the O2 adsorption. The adsorption energies of the O2 and *OOH intermediates are proportional to the H2O2 selectivity (64.39%), higher than that of the CNT (37.81%). With the simple and durable production of H2O2 by IBU@CNT-EM electrofiltration, the permeate can actuate Fenton oxidation to efficiently decompose emerging pollutants and inactivate bacteria. Our study introduces a new paradigm for developing high-performance H2O2-production membranes for water treatment by reusing environmental functional materials.

Ecological risk assessment methods for oxidative by-products in the oxidation degradation process of emerging pollutants: A review.

The inherent toxicity and persistence of emerging contaminants such as antibiotics and endocrine disruptors pose substantial threats to the environment. Advanced oxidation processes (AOPs) employed for oxidative degradation could yield toxic oxidation by-products (OBPs), including organic acids and aromatic hydrocarbons. Despite their typically low concentrations, OBPs require scrutiny owing to their potential health risks. Although effective assessment methodologies are available, a comprehensive review focusing on the ecological and environmental effects of these pollutants is lacking. This study offers a succinct overview of existing ecotoxicological exposure assessments for emerging organic pollutants. Further, it encapsulates principal dose-response assessment techniques and provides a comparative analysis of several methods. The straightforward assessment factor method evaluates risk based on exposure and species sensitivity and is suitable for preliminary assessments of single pollutants; Species Sensitivity Distribution (SSD) compares species sensitivities to OBPs, emphasizing the importance of species-specific toxicological responses; microcosm and mesocosm methods simulate and predict the effects of OBPs on aquatic life by considering environmental diversity and biological community structures and are ideal for assessing the toxicity of multiple OBPs; the ecological risk analysis model employs mathematical and probabilistic approaches to comprehensively and accurately assess exposures and effects, accounting for the complexities and uncertainties inherent in ecotoxicological evaluations. Different risk characterization techniques are outlined in this study, including the risk quotient (RQ), which is ideal for quantifying and comparing risks; probabilistic ecological risk assessment (PERA), suitable for managing significant uncertainty; and the Environmental Pollution Index (EPI), the preferred method for quantitative assessment of OBP pollution levels. The merits and limitations of each of these quantitative assessment tools are evaluated, providing a comprehensive view of their applications in risk analysis. In addition, pressing contemporary challenges are identified and trajectories and pivotal issues suggested for future research.

Development of tungsten-modified iron oxides to decompose an over-the-counter painkiller, Acetaminophen by activating peroxymonosulfate.

Acetaminophen (APAP) is a well-known type of over-the-counter painkillers and is frequently found in surface waterbodies, causing hepatotoxicity and skin irritation. Due to its persistence and chronic effects on the environment, innovative solutions must be provided to decompose APAP, effectively. Innovative catalysts of tungsten-modified iron oxides (TF) were successfully developed via a combustion method and thoroughly characterized using SEM, TEM, XRD, XPS, a porosimetry analysis, Mössbauer spectroscopy, VSM magnetometry, and EPR. With the synthesis method, tungsten was successfully incorporated into iron oxides to form ferrites and other magnetic iron oxides with a high porosity of 19.7 % and a large surface area of 29.5 m2/g. Also, their catalytic activities for APAP degradation by activating peroxymonosulfate (PMS) were evaluated under various conditions. Under optimal conditions, TF 2.0 showed the highest APAP degradation of 95 % removal with a catalyst loading of 2.0 g/L, initial APAP concentration of 5 mg/L, PMS of 6.5 mM, and pH 2.15 at room temperature. No inhibition by solution pHs, alkalinity, and humic acid was observed for APAP degradation in this study. The catalysts also showed chemical and mechanical stability, achieving 100 % degradation of 1 mg/L APAP during reusability tests with three consecutive experiments. These results show that TFs can effectively degrade persistent contaminants of emerging concern in water, offering an impactful contribution to wastewater treatment to protect human health and the ecosystem.

Innovative techniques for combating a common enemy forever chemicals: A comprehensive approach to mitigating per- and polyfluoroalkyl substances (PFAS) contamination.

The pervasive presence of per and polyfluoroalkyl substances (PFAS), commonly referred to as "forever chemicals," in water systems poses a significant threat to both the environment and public health. PFAS are persistent organic pollutants that are incredibly resistant to degradation and have a tendency to accumulate in the environment, resulting in long-term contamination issues. This comprehensive review delves into the primary impacts of PFAS on both the environment and human health while also delving into advanced techniques aimed at addressing these concerns. The focus is on exploring the efficacy, practicality, and sustainability of these methods. The review outlines several key methods, such as advanced oxidation processes, novel materials adsorption, bioremediation, membrane filtration, and in-situ chemical oxidation, and evaluates their effectiveness in addressing PFAS contamination. By conducting a comparative analysis of these techniques, the study aims to provide a thorough understanding of current PFAS remediation technologies, as well as offer insights into integrated approaches for managing these persistent pollutants effectively. While acknowledging the high efficiency of adsorption and membrane filtration in reducing persistent organic pollutants due to their relatively low cost, versatility, and wide applicability, the review suggests that the integration of these methods could result in an overall enhancement of removal performance. Additionally, the study emphasizes the need for researcher attention in key areas and underscores the necessity of collaboration between researchers, industry, and regulatory authorities to address this complex challenge.

Micro and nanobubbles-assisted advanced oxidation processes for water decontamination: The importance of interface reactions.

Micro and nanobubbles (MNBs), as an efficient and convenient method, have been widely used in water treatment. Composed of gas and water, MNBs avoid directly introducing potential secondary pollutants. Notably, MNBs exhibit significant advantages through interface reactions in assisting AOPs. They overcome barriers like low mass transfer coefficients and limited reactive sites, and shorten the distance between pollutants and oxidants, achieving higher pollutant removal efficiency. However, there is a lack of systematic summary and in-depth discussion on the fundamental mechanisms of MNBs-assisted AOPs. In this critical review, the characteristics of MNBs related to water treatment are outlined first. Subsequently, the recent applications, performance, and mechanisms of MNBs-assisted AOPs including ozone, plasma, photocatalytic, and Fenton oxidation are overviewed. We conclude that MNBs can improve pollutant removal mainly by enhancing the utilization of reactive oxygen species (ROS) generated by AOPs due to the effective interface reactions. Furthermore, we calculated the electrical energy per order of reaction (EE/O) parameter of different MNBs-assisted AOPs, suggesting that MNBs can reduce the total energy consumption in most of the tested cases. Finally, future research needs/opportunities are proposed. The fundamental insights in this review are anticipated to further facilitate an in-depth understanding of the mechanisms of MNBs-assisted AOPs and supply critical guidance on developing MNBs-based technologies for water treatment.

Overlooked role of CO3·- reactivity with different dissociation forms of organic micropollutants in degradation kinetics modeling: A case study of fluoxetine degradation in a UV/peroxymonosulfate system.

Selective oxidizing agent carbonate radical (CO3•-) is an important secondary radical in radical-based advanced oxidation technology for wastewater treatment. However, the role of CO3•- in removing ionizable organic micropollutants (OMs) under environmentally relevant conditions remains unclear. Herein we investigated CO3•- effect on degradation kinetics of fluoxetine in UV/peroxymonosulfate (PMS) system based on a built radical model considering CO3•- reactivity differences with its different dissociation forms. Results revealed that the model, which incorporated CO3•- selective reactivity (with determined second-order rate constants, ksrc,CO3·-, of 7.33 ×106 and 2.56 ×108 M-1s-1 for cationic and neutral fluoxetine, respectively) provided significantly more accurate predictions of fluoxetine degradation rates (k). A good linear correlation was observed between ksrc,CO3·- from experiments and literatures for 24 ionizable OMs and their molecular orbital energy gaps and oxidation potentials, suggesting the possible electron transfer reaction mechanism. Cl- slightly reduced the degradation rates of fluoxetine owing to rapid transformation of Cl• with HCO3- into CO3•-, which partially compensated for the quenching effects of Cl- on HO• and SO4•-. Dissolved organic matter significantly quenched reactive radicals. The constructed kinetic model successfully predicted fluoxetine degradation rates in real waters, with CO3•- being the dominant contributor (∼90 %) to this degradation process.

Transforming wastewater treatment: Recent advancements in Catalytic Wet Air Oxidation with pillared clay catalysts for phenol remediation.

Catalytic Wet Air Oxidation (CWAO) has recently been recognized as a promising technique for degrading persistent organic pollutants, such as phenol, in wastewater. Among various catalysts, Pillared Interlayer Clays (PILCs) stand out due to their high specific surface area and porous nature. This review delves into the latest progress in CWAO processes utilizing PILCs for the degradation of organic contaminants such as phenol in wastewater. It meticulously assesses the synthesis of PILCs, and their structural properties, including monolithic forms, to understand their effect on catalyst efficiency. Key insights into how these attributes affect the phenol degradation rate and the CWAO process's stability are discussed, providing crucial direction for enhancing catalyst performance. The review highlights the significance of choosing catalysts that offer a balance between cost-efficiency and operational efficacy under mild conditions. The recent results are reported, summarized, and compared, thus proving the feasibility of using PILCs as promising materials for phenol removal. The reaction parameters, phenol conversion, and degradation mechanisms are highlighted. The catalytic efficiency of PILCs was significantly affected by the synthesis methods and reaction parameters, and outperformed most costly catalysts. PILCs are highlighted as especially advantageous catalysts, offering strong performance at lower costs, which boosts the up-scaling opportunities of CWAO methods. This analysis also points out research gaps and proposes directions for future studies, such as exploring innovative PILC synthesis methods to improve their catalytic effectiveness and durability further. It stresses the need to incorporate environmental and sustainability considerations into catalyst design and selection, aligning with the principles of green chemistry in wastewater treatment. Finally, we conclude that proposing new directions for PILCs in CWAO in further naturally-based surface modifications, is also a promising approach for PILCs to perform more efficiently.

Single-atom catalysts activate persulfate to degrade emerging organic contaminants in aqueous environments.

Single-atom catalysts (SACs) exhibit outstanding catalytic activity due to their highly dispersed metal centers. Activating persulfates (PS) with SACs can generate various reactive oxygen species (ROS) to efficiently degrade emerging organic contaminants (EOCs) in aqueous environments, offering unique advantages such as high reaction rates and excellent stability. This technique has been extensively researched and holds enormous potential applications. In this paper, we comprehensively elaborated on the synthesis methods of SACs and their limitations, and factors influencing the catalytic performance of SACs, including metal center characteristics, coordination environment, and types of substrates. We also analyzed practical considerations for application. Subsequently, we discussed the mechanism of SACs activating PS for EOCs degradation, encompassing adsorption processes, radical pathways, and non-radical pathways. Finally, we provide prospects and outline our vision for future research, aiming to guide advancements in applying this technique.

Catalytic Degradation of Bisphenol A with a Magnetically Recoverable Geopolymer Composite Using Coal Gangue.

The widespread presence and use of Bisphenol A (BPA) in aquatic environments has caused significant ecological damage. Coal gangue (CG), a byproduct of coal mining, poses a major environmental concern due to its vast land occupation and potential for pollution. A magnetic recyclable geopolymer (MnFe2O4-CGP) using coal gangue geopolymer (CGP) as the carrier was successfully synthesized and was evaluated for its ability to Fenton-like degrade BPA. The characterization techniques revealed the successful incorporation of spherical MnFe2O4 onto the CGP surface and that CGP serves as an excellent platform for the immobilization and dispersion of MnFe2O4. The degradation rate reached 100% within 60 min at pH = 5, 15 mmol/L H2O2, 0.6 g/L catalyst, and 50 mg/L BPA, significantly higher than MnFe2O4 and CGP alone. It was indicated that the degradation rate of BPA in MnFe2O4-CGP composites was 0.1121 min-1, which was consistent with the first-order kinetic model. The saturation magnetization of MnFe2O4-CGP was measured to be 10.96 emu/g, enabling convenient recovery. MnFe2O4-CGP exhibited excellent stability, as the degradation rate of BPA remained above 95% even after five reaction cycles. This efficiency may be due to the MnFe2O4-CGP induced generation of reactive radicals. Quenching and EPR radical trapping experiments unequivocally confirmed that the reactive radical was hydroxyl radical (•OH). These results indicate that MnFe2O4-CGP has potential application prospects as a magnetic recyclable geopolymer composite in Fenton-like catalysis.

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

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

Discovery of an End-to-End Pattern for Contaminant-Oriented Advanced Oxidation Processes Catalyzed by Biochar with Explainable Machine Learning.

The utilization of biochar-catalyzed peroxymonosulfate in advanced oxidation processes (BC-PMS AOPs) is widely acknowledged as an effective and economical method for mitigating emerging contaminants (ECs). Especially, state-of-the-art machine learning (ML) technology has been employed to accurately predict the reaction rate constants of EC degradation in BC-PMS AOPs, primarily focusing on three aspects: performance prediction, operating condition optimization, and mechanism interpretation. However, its real application in specific degradation optimization targeting different ECs is seldom considered, hindering the realization of contaminant-oriented BC-PMS AOPs. Herein, we propose a hierarchical ML pipeline to achieve an end-to-end (E2E) pattern for addressing this issue. First, the overall XGB model, trained with the comprehensive data set, can perform well in predicting the reaction constants of EC degradation in BC-PMS AOPs, additionally providing the basis for further analysis of various ECs. Then, the submodels trained with different EC clusters can offer specific strategies for the selection of the optimum option for BC-PMS AOPs of specific ECs with different HOMO-LUMO gaps, thus forming an E2E operating pattern for BC-PMS AOPs. This study not only increases our understanding of contaminant-oriented optimization of AOPs but also successfully bridges the gap between ML model development and its environmental application.

Bridge-oxygen bonding modulates Ru single atoms for peroxymonosulfate activation: Importance of high-valent Ru species and 1O2.

The application of single-atom catalysts (SACs) to advanced oxidation processes (AOPs) based on peroxymonosulfate (PMS) has attracted considerable attention. However, the catalytic pathways and mechanisms underlying these processes remain unclear. In this study, NiFe-LDH was synthesized and single Ru atoms were stably loaded onto it by forming Ru-O-M (M=Ni or Fe) bonds (Ru@NiFe-LDH). This was demonstrated using high-angle annular dark-field scanning TEM (HAADF-STEM) and X-ray absorption fine structure spectra (XANES). The Ru@NiFe-LDH/PMS system showed a high catalytic reactivity (100 % sulfamethoxazole degradation in only 30 min), high stability (97 % reactivity was maintained after continuous operation for 400 min), and wide pH suitability (working pH range 3-11) for AOPs. The crucial roles of the high-valent species (Ru(V) = O) and 1O2 in this reaction were verified. Density functional theory (DFT) calculations revealed that electron transfer produced a positively charged Ru. This enhances the adsorption of negatively charged PMS anions onto the Ru monoatomic sites, thereby, causing the formation of Ru-PMS* complexes. This study implies that the structure-function relationship between organic compounds and SACs plays a significant role in PMS-based AOPs, and provides a comprehensive mechanism for the role of high-valent species in heterogeneous Fenton-like systems.