Journal of hazardous materials最新文献

Long-range electron transfer pathways at FeCu bimetallic interfaces: Bridging catalytic mechanisms and scalable applications for persistent pollutant degradation. FeCu双金属界面上的远程电子转移途径：桥接催化机制和可扩展的污染物降解应用。

Journal of hazardous materials Pub Date : 2025-08-15 Epub Date: 2025-05-22 DOI: 10.1016/j.jhazmat.2025.138682

Xiaoyin You, Chaohai Wang, Chuqiao Wang, Xing Xu, Yuying Hu, Ning Li, Fengping Hu, Wen Liu, Xiaoming Peng

{"title":"Long-range electron transfer pathways at FeCu bimetallic interfaces: Bridging catalytic mechanisms and scalable applications for persistent pollutant degradation.","authors":"Xiaoyin You, Chaohai Wang, Chuqiao Wang, Xing Xu, Yuying Hu, Ning Li, Fengping Hu, Wen Liu, Xiaoming Peng","doi":"10.1016/j.jhazmat.2025.138682","DOIUrl":"10.1016/j.jhazmat.2025.138682","url":null,"abstract":"Efficient and stable heterogeneous catalysts for peroxymonosulfate (PMS) activation are pivotal for advancing advanced oxidation processes in water treatment. However, the limited redox cycling capacity of single-metal sites often hinders their catalytic performance and durability. Here, dispersed Fe-Cu bimetallic clusters anchored on a nitrogen-sulfur codoped carbon matrix ((FeCu-SNC) were synthesized via a coordination-pyrolysis strategy. FeCu-SNC was engineered to activate peroxymonosulfate (PMS) for the degradation of bisphenol A (BPA) and structurally diverse pollutants. Combined experimental and density functional theory (DFT) analyses revealed that the Fe-Cu dual sites synergistically enhanced PMS adsorption and triggered a dominant electron transfer pathway (ETP), bypassing conventional radical-mediated mechanisms. The FeCu-SNC/PMS system achieved rapid BPA degradation (kobs > 0.38 min-1), with preferential oxidation of pollutants bearing electron-donating groups. A dynamic catalytic membrane system (DCMS) integrated with electrospinning technology enabled catalyst reuse, maintaining > 95 % BPA removal over 300 min of continuous operation. Furthermore, a scalable ETP device utilizing a salt bridge and ammeter effectively isolated sulfate ion leaching, attaining 96 % pollutant removal after 72 h while addressing secondary pollution. This work provides a dual strategy- catalyst design and process engineering-for sustainable water decontamination.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"494 ","pages":"138682"},"PeriodicalIF":0.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144133333","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanochemical degradation of UV-328 by solid oxidative reagents: Peroxydisulfate vs. peroxymonosulfate. 固体氧化试剂对UV-328的机械化学降解：过氧硫酸氢盐vs过氧单硫酸氢盐。

Journal of hazardous materials Pub Date : 2025-08-15 Epub Date: 2025-06-03 DOI: 10.1016/j.jhazmat.2025.138715

Xiwang Zhao, Xitao Liu, Jun Huang, Chunye Lin, Mengchang He, Wei Ouyang

{"title":"Mechanochemical degradation of UV-328 by solid oxidative reagents: Peroxydisulfate vs. peroxymonosulfate.","authors":"Xiwang Zhao, Xitao Liu, Jun Huang, Chunye Lin, Mengchang He, Wei Ouyang","doi":"10.1016/j.jhazmat.2025.138715","DOIUrl":"10.1016/j.jhazmat.2025.138715","url":null,"abstract":"Peroxydisulfate (PDS) and peroxymonosulfate (PMS) are crucial oxidative additives for mechanochemical (MC) treatment of persistent organic pollutants and contaminated soils. However, their differences between solid-phase mechanisms remain unclear. This study found that both PDS and PMS achieved comparable 2-(2H-Benzotriazol-2-yl)-4,6-bis(2-methyl-2-butanyl)phenol (UV-328) degradation (91.9 % in PDS and 94.1 % in PMS after 120 min of milling), but the variance observed at elevated milling intensities and persulfate-to-UV-328 mass ratios implies that PDS and PMS follow different working regimes. Alterations in surface-physicochemistry and structure of PDS are more pronounced than those of PMS. Conversely, PMS shows more obvious changes in infrared properties, presumably forming hydrogen bonds with the hydroxyl group of UV-328. Probe experiments, with quantum chemical calculations, indicate that PDS is more likely than PMS to achieve O-O bond cleavage to generate sulfate radicals, while PMS depends on direct oxidation capabilities to selectively oxidize electron-rich pollutants. Ultimately, PDS exhibited stronger mineralization efficiency (13.20 %) and more small-molecule production (e.g., benzotriazole, NH4+) compared to PMS (9.87 %). Concerningly, both systems result in oligomer formation (more ethers in PDS, while more esters and ethers in PMS). This work may provide foundational knowledge for the MC treatment of organic waste with persulfates as co-milling agents.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"494 ","pages":"138715"},"PeriodicalIF":0.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144228073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synergistic effects of sulfur-doped carbon dots/permanganate process for DCF degradation: Mechanism and pathways. 硫掺杂碳点/高锰酸盐工艺对DCF降解的协同效应：机理与途径。

Journal of hazardous materials Pub Date : 2025-08-15 Epub Date: 2025-05-21 DOI: 10.1016/j.jhazmat.2025.138567

Danmei Luo, Heng Zhang, Xingxing An, Jia Zhao, Can Feng, Jialong Yin, Mengfan Luo, Tao Wei, Yang Liu, Yanbiao Shi, Jing Zhang, Bo Lai

{"title":"Synergistic effects of sulfur-doped carbon dots/permanganate process for DCF degradation: Mechanism and pathways.","authors":"Danmei Luo, Heng Zhang, Xingxing An, Jia Zhao, Can Feng, Jialong Yin, Mengfan Luo, Tao Wei, Yang Liu, Yanbiao Shi, Jing Zhang, Bo Lai","doi":"10.1016/j.jhazmat.2025.138567","DOIUrl":"10.1016/j.jhazmat.2025.138567","url":null,"abstract":"Extensive research has explored strategies to enhance permanganate (PM) oxidation capacity, with carbon materials having shown significant promise in treating refractory organic pollutants in water. However, the impacts of carbon quantum dots (CQDs) and heteroatom-doped CQDs on PM oxidation remain unclear, warranting further investigation. In this study, we found that sulfur-doped CQDs (SCQDs) significantly outperformed CQDs, nitrogen-doped CQDs (NCQDs), and boron-doped CQDs (BCQDs) in promoting the oxidation reaction of diclofenac sodium (DCF) by PM. Through quenching experiments, light-shielding tests, and UV-Vis spectroscopy, we revealed that the PM/SCQDs system could rapidly and stably generate Mn(III) and MnO2, thereby facilitating the removal of DCF. Characterization analysis showed that SCQDs possess a surface enriched with diverse functional groups, and sulfur doping further enhances their electron cloud density. This structural characteristic enhances the ability of SCQDs to donate electrons to permanganate, thereby promoting its reduction to Mn(III) and MnO2. A comprehensive evaluation of key operational parameters governing the PM/SCQDs system performance was conducted. Additionally, the PM/SCQDs system exhibited substantial resistance to interference from common matrix ions and natural organic matter in water. The study provides a new perspective on enhancing permanganate oxidation by SCQDs and offers a promising pathway for efficient water pollutant degradation.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"494 ","pages":"138567"},"PeriodicalIF":0.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144096332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Integrative analysis of microbiome and metabolome reveals the effect of deoxynivalenol on growth performance, liver and intestinal health of largemouth bass (Micropterus salmoides). 微生物组学和代谢组学综合分析揭示了脱氧雪腐镰刀菌醇对大口黑鲈生长性能、肝脏和肠道健康的影响。

Journal of hazardous materials Pub Date : 2025-07-05 DOI: 10.1016/j.jhazmat.2025.139148

Yi Lian Yin, You Xing Xu, Meng Ting Wang, Dao Zhi Yang, Xiao Yan Wang, Xian Ke Zhou, Meng Meng Huang, Shun Yang, Hui Fei

{"title":"Integrative analysis of microbiome and metabolome reveals the effect of deoxynivalenol on growth performance, liver and intestinal health of largemouth bass (Micropterus salmoides).","authors":"Yi Lian Yin, You Xing Xu, Meng Ting Wang, Dao Zhi Yang, Xiao Yan Wang, Xian Ke Zhou, Meng Meng Huang, Shun Yang, Hui Fei","doi":"10.1016/j.jhazmat.2025.139148","DOIUrl":"https://doi.org/10.1016/j.jhazmat.2025.139148","url":null,"abstract":"This study explored the toxic effects of deoxynivalenol (DON) intake at low (100 µg·Kg-1, LD group) and high doses (300 µg·Kg-1, HD group) on largemouth bass (Micropterus salmoides). After a 56-day feeding trial, the HD group exhibited significantly reduced growth performance and weakened antioxidant capacity, along with elevated activities of enzymes related to metabolic dysregulation. Histopathological analysis showed an increase in hepatic cell vacuoles, as well as a shortened intestinal villi in both LD and HD groups. Notably, high-dose DON intake markedly down-regulated the expression of intestinal epithelial tight junction-related genes and proteins. Microbiome analysis indicated a significant increase in the Delftia and Acinetobacteria relative abundance, accompanied by diminished in Mycoplasma abundance in the HD group. Metabolomic profiling demonstrated that the dysregulated metabolites were mainly associated with the lysine biosynthesis pathway. Integrative multi-omics analysis revealed that pyridoxamine and diferuloylputrescine served as key biomarkers associated with Acinetobacteria. Collectively, we confirmed that high-dose DON intake induces hepatointestinal damage, thereby impairing the growth performance of largemouth bass. Our findings also further highlighted the link between DON-induced gut microbiota alterations and metabolic disorders, offering new intervention targets for alleviating DON toxicity.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"495 ","pages":"139148"},"PeriodicalIF":0.0,"publicationDate":"2025-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144577448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Peracetic acid concentration-driven active species switching in sulfur-modified iron-doped graphitic carbon nitride for adaptive degradation of organics. 过氧乙酸浓度驱动的硫修饰铁掺杂石墨氮化碳自适应降解活性物质切换。

Journal of hazardous materials Pub Date : 2025-07-04 DOI: 10.1016/j.jhazmat.2025.139063

Jun Li, Hailing Zhao, Yi Ren, Chao Liu, Longguo Li, Bo Lai

{"title":"Peracetic acid concentration-driven active species switching in sulfur-modified iron-doped graphitic carbon nitride for adaptive degradation of organics.","authors":"Jun Li, Hailing Zhao, Yi Ren, Chao Liu, Longguo Li, Bo Lai","doi":"10.1016/j.jhazmat.2025.139063","DOIUrl":"https://doi.org/10.1016/j.jhazmat.2025.139063","url":null,"abstract":"Herein, a sulfur-modified iron-doped g-C3N4 composite (FSCN) was synthesized to activate peracetic acid (PAA) for organic micropollutant degradation. The FSCN/PAA system demonstrated exceptional catalytic performance surpassing control catalysts, achieving effective removal of multiple contaminants containing diverse electron-donating and -withdrawing functional groups. The results of quenching experiments and spectroscopic characterization analyses revealed concentration-dependent active species generation: hydroxyl radicals (HO•) predominated at low PAA concentrations (25 μM), whereas high-valent iron species (Fe(IV/V)) became dominant at elevated PAA levels (400 μM). This distinctive switching behavior stems from the dual catalytic functionality of FSCN, which simultaneously activates PAA to generate Fe(IV/V) while catalyzing H2O2 decomposition to produce HO•. The practicability of FSCN/PAA system was systematically validated through real wastewater treatment and continuous flow operation, and the results indicate that the system showed robust environmental compatibility. This work establishes a novel concentration-dependent active species regulation strategy through rational catalyst design and PAA dosage control, providing fundamental insights and technological advancement for advanced oxidation processes in water remediation.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"495 ","pages":"139063"},"PeriodicalIF":0.0,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144568278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Removal of pharmaceuticals through UV-C/Performic acid advanced oxidation process: Kinetics and identification of reactive species. 通过UV-C/过甲酸深度氧化法去除药物：动力学和活性物质的鉴定。

Journal of hazardous materials Pub Date : 2025-07-03 DOI: 10.1016/j.jhazmat.2025.139016

Christelle Nabintu Kajoka, Stephan Brosillon, Corine Reibel, Yacine Khadija Diop, Marcos Oliveira, Vincent Rocher, Ghassan Chebbo, Johnny Gasperi, Julien Le Roux

{"title":"Removal of pharmaceuticals through UV-C/Performic acid advanced oxidation process: Kinetics and identification of reactive species.","authors":"Christelle Nabintu Kajoka, Stephan Brosillon, Corine Reibel, Yacine Khadija Diop, Marcos Oliveira, Vincent Rocher, Ghassan Chebbo, Johnny Gasperi, Julien Le Roux","doi":"10.1016/j.jhazmat.2025.139016","DOIUrl":"https://doi.org/10.1016/j.jhazmat.2025.139016","url":null,"abstract":"Performic acid (PFA), widely recognized for its disinfectant properties in wastewater, shows selective and limited reactivity in oxidizing micropollutants. This study investigates the activation of PFA through UV-C photolysis to generate an advanced oxidation process (UV-C/PFA) and enhance the degradation of six pharmaceuticals: lidocaine, furosemide, sulfamethoxazole, diclofenac, acetaminophen, and carbamazepine. The synergy of UV-C photolysis with PFA enhances the removal of PFA-persistent pharmaceuticals. For instance, diclofenac, acetaminophen, and sulfamethoxazole, initially unreactive with PFA, were entirely degraded within ten minutes under UV-C/PFA in a phosphate buffer solution. This increased reactivity results from generated reactive species like hydroxyl (HO•), peroxyl (R-O•) radicals and singlet oxygen (1O2), confirmed by electron paramagnetic resonance, with HO• primarily originating from the background H2O2 present in the PFA solution. While UV-C/PFA produced fewer HO• than UV-C/H2O2, it has distinct advantages through the selective action of 1O2 and R-O• in degrading some pharmaceuticals. 1O2 was also detected in the PFA solution and could explain its selective reactivity, especially with compounds containing reduced sulfur or tertiary amine groups. Overall, UV-C/PFA yields transformation products of lower molar mass compared to PFA, thus potentially increasing mineralization. In wastewater effluent, UV-C/PFA improved pharmaceutical degradation, though scavenging effects by wastewater constituents reduced removal rates.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"495 ","pages":"139016"},"PeriodicalIF":0.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144565581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

²¹⁰Pb chronology assessing the historical microplastics dynamics and aging effects in urban areas with separate sewer systems and multiple-use reservoir. 210Pb年代学评估城市地区独立下水道系统和多用途水库的微塑料动态和老化效应。

Journal of hazardous materials Pub Date : 2025-07-01 DOI: 10.1016/j.jhazmat.2025.139118

Fabiano T Conceição, Alexandre M Fernandes, Sarah G Lacerda, Rodrigo B Moruzzi, Naiara O Santos, Rosa Busquets, Luiza C Campos

{"title":"210Pb chronology assessing the historical microplastics dynamics and aging effects in urban areas with separate sewer systems and multiple-use reservoir.","authors":"Fabiano T Conceição, Alexandre M Fernandes, Sarah G Lacerda, Rodrigo B Moruzzi, Naiara O Santos, Rosa Busquets, Luiza C Campos","doi":"10.1016/j.jhazmat.2025.139118","DOIUrl":"https://doi.org/10.1016/j.jhazmat.2025.139118","url":null,"abstract":"This study uses the 210Pb chronology to assess the historical dynamics and aging effects of microplastics (MPs) in urban areas with separate sewer systems and multiple-use reservoir for the first time, reconstructing their temporal deposition over multiple decades. The Sorocaba River basin, state of São Paulo, Brazil, was chosen as study area. Direct release of untreated urban sewage and stormwater runoff was the main source of MPs in riverbed sediments before 2006. The construction of wastewater treatment plants (WWTPs) post-2006 led to a decrease in fibres, films, fragments, and pellets. Despite the new WWTPs, the levels of tyre wear particles continued to rise, reaching ∼ 85,000 units/kg at SP4 in 2011, due to an increase of vehicle numbers circulating in impervious surfaces in the cities of this watershed. However, the total of MPs decreased along the multiple-use reservoir, from ∼ 43,000 to ∼ 6300 units/kg at SP1 and SP3, respectively. Using pollution load index, nearly all sediment cores were classified to have extremely high pollution levels. Combining 210Pb chronology and sediment pollution of MPs has been useful in exposing historical deposition patterns of MPs in urban areas and multiple-use reservoir environments and relating them to interventions made to mitigate pollution.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"495 ","pages":"139118"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144562443","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electro-pulsation-generated variable-valent metal triggers alternate pesticide oxidation-chlorinated byproduct reduction on ruthenium-single-atom electrode. 电脉冲产生的可变价金属在钌单原子电极上触发农药氧化-氯化副产物的交替还原。

Journal of hazardous materials Pub Date : 2025-06-26 DOI: 10.1016/j.jhazmat.2025.139052

Yangqi E, Binyao Wang, Yibo Lin, Huachang Jin, Xueming Chen, Jianmeng Chen, Jin Hur, Yang Yu, Dongzhi Chen

{"title":"Electro-pulsation-generated variable-valent metal triggers alternate pesticide oxidation-chlorinated byproduct reduction on ruthenium-single-atom electrode.","authors":"Yangqi E, Binyao Wang, Yibo Lin, Huachang Jin, Xueming Chen, Jianmeng Chen, Jin Hur, Yang Yu, Dongzhi Chen","doi":"10.1016/j.jhazmat.2025.139052","DOIUrl":"https://doi.org/10.1016/j.jhazmat.2025.139052","url":null,"abstract":"Anodic oxidation presents a compelling strategy for pesticide-contained wastewater treatment. However, due to the reactive chlorine species-induced side reactions, toxic chlorinated byproducts are prevalent. Herein, a MOF derivative Ru-single-atom electrode, Ru-SbOX, was specialized for use in electro-pulsation to realize pesticide degradation and in-situ byproduct elimination. The introduction of single-atomic Ru promoted pseudocapacitive Run+-Sbn+ redox conversion, electro-creating metastable high-valent Sb5+ and low-valent Sb3+, then triggering the •OH and •H generation during anodic and cathodic cycles, respectively. This beneficially created an alternating oxidation-reduction environment in an identical electrode, leading to alternate pesticide degradation-byproduct elimination. These allowed Ru-SbOX to achieve a super-prominent normalized phoxim degradation kinetics constant (3.1 × 10-6 m·s-1) in anodic cycles, surpassing other state-of-the-art electrodes; meanwhile, the reactive chlorine species-induced chlorinated byproducts and even N, S, P-related byproducts were in-situ eliminated by at least 10 times in cathodic cycles. This work provides a new perspective for tuning the valence-variable metal in the single-atom electrode to achieve efficient pesticide degradation and in-situ byproduct elimination using the electro-pulsation method.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"495 ","pages":"139052"},"PeriodicalIF":0.0,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144512978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unveiling non-radical oxidation pathways in peroxymonosulfate/cobalt(II) systems: Critical role of cobalt(III) and cobalt(IV) explored by manganese(II) probing. 揭示过氧单硫酸盐/钴（II）系统中的非自由基氧化途径：通过锰（II）探测探索钴（III）和钴（IV）的关键作用。

Journal of hazardous materials Pub Date : 2025-06-25 DOI: 10.1016/j.jhazmat.2025.139014

Luwei Li, Xuecong Qian, Shilong Wang, Yun Liu, Da Wang, Huixin Zhang, Yechen An, Haijun Cheng, Jun Ma

{"title":"Unveiling non-radical oxidation pathways in peroxymonosulfate/cobalt(II) systems: Critical role of cobalt(III) and cobalt(IV) explored by manganese(II) probing.","authors":"Luwei Li, Xuecong Qian, Shilong Wang, Yun Liu, Da Wang, Huixin Zhang, Yechen An, Haijun Cheng, Jun Ma","doi":"10.1016/j.jhazmat.2025.139014","DOIUrl":"https://doi.org/10.1016/j.jhazmat.2025.139014","url":null,"abstract":"While non-radical Co species are recognized as critical intermediates in peroxymonosulfate (PMS)/Co(II) systems, their speciation and formation pathways remain under debate. In this study, Mn(II), characterized by well-defined redox behavior and mild reactivity toward radical species, was employed as a mechanistic probe to elucidate the activation mechanism of the PMS/Co(II) system under near-neutral conditions. Trace Co(II) (1 µM) accelerated Mn(II) oxidation kinetics by over 2000-fold at pH 8.0 compared to PMS alone. Scavenging experiments and near-100 % PMS utilization efficiency confirmed a non-radical mechanism. Co(IV) was proposed as the primary reactive species. Mn(III) capture experiments and density functional theory calculations indicated that Co(IV) oxidized Mn(II) via single-electron transfer. The derived Co(III) byproduct further contributed to Mn(II) oxidation, with reaction rates of 1.06 × 105 M-1·s-1 at pH 5.5 and 1.20 × 105 M-1·s-1 at pH 8.0. Kinetic modeling validated this pathway, quantifying the Co(IV)-Mn(II) reaction rates as 2.88 × 106 M-1·s-1 (pH 5.5) and 2.57 × 106 M-1·s-1 (pH 8.0). Under the experimental conditions, Co(III) and Co(IV) contributed comparably to Mn(II) oxidation. Mn(II)-probing experiments revealed that organic contaminant degradation was governed by substrate-dependent competition among three key reactive species: Co(II)-PMS complexes, high-valent cobalt species, and radicals. These findings provided mechanistic insights into PMS/Co(II) activation and further confirmed its potential for efficient manganese removal in water treatment.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"495 ","pages":"139014"},"PeriodicalIF":0.0,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144510072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Efficient and stable copper tungstate catalyst for water treatment with peroxymonosulfate: Effect of synthetic pH, primary oxidant, and practical feasibility. 高效稳定的钨酸铜过氧单硫酸盐水处理催化剂：合成pH、主氧化剂的影响及实际可行性。

Journal of hazardous materials Pub Date : 2025-05-05 Epub Date: 2025-02-08 DOI: 10.1016/j.jhazmat.2025.137482

Khen Duy Tran, Yong-Yoon Ahn, Bomi Kim, Kitae Kim, Jonghun Lim, Jungwon Kim

{"title":"Efficient and stable copper tungstate catalyst for water treatment with peroxymonosulfate: Effect of synthetic pH, primary oxidant, and practical feasibility.","authors":"Khen Duy Tran, Yong-Yoon Ahn, Bomi Kim, Kitae Kim, Jonghun Lim, Jungwon Kim","doi":"10.1016/j.jhazmat.2025.137482","DOIUrl":"10.1016/j.jhazmat.2025.137482","url":null,"abstract":"In this study, copper tungstate (CuWO4) nanoparticles, which are highly efficient and stable catalysts for water treatment, were synthesized via a hydrothermal method under various pH conditions. CuWO4 synthesized at pH 10 (CuWO4@10) exhibited the highest degradation efficiency and the lowest metal ion leaching. In the presence of CuWO4@10 (0.5 g/L) and peroxymonosulfate (PMS, 1 mM), 4-chlorophenol (4-CP, 100 μM) was completely degraded within 5 min, and the total metal ion leaching concentration after 4 h was only 10.2 μM. The catalytic activity of CuWO4 for 4-CP degradation was 4.7-99.0 times greater than that of CuO catalysts. This enhanced performance is attributed to the presence of W, which increases the surface area and reduces charge transfer resistance. Based on the results of radical-quenching experiments, solvent exchange experiments, PMS decomposition measurements, electron paramagnetic resonance spectroscopy, and Raman spectroscopy, high-valent copper (Cu(III)) was identified as the primary oxidant responsible for degradation in the CuWO4/PMS system. The CuWO4/PMS system rapidly degraded various phenolic compounds, and its degradation efficiency remained consistent across repeated uses of the CuWO4 catalyst. Degradation in groundwater also occurred efficiently in the CuWO4/PMS system. This study provides valuable insights into the development of practical PMS-based water treatment processes.","PeriodicalId":94082,"journal":{"name":"Journal of hazardous materials","volume":"488 ","pages":"137482"},"PeriodicalIF":0.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143384518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0