RSC Advances
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2024
·Vol. 14
·期 24
·16727-16735
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IF 3.9
Huizhong Wu,Qiong Yi,Xiang Li,Yingxi Wang,Ling Li
Low catalytic efficiency and catalyst recovery are the key factors limiting the practical application of advanced oxidation processes. In this work, a core–shell magnetic nanostructure Fe3O4@MIL-101(Fe, Co) was prepared via a simple solvothermal method. The core–shell structure and magnetic recovery performance were characterized by various technologies. The results of dye degradation experiments proved that within 10 minutes, the Fe3O4@MIL-101(Fe, Co)/PMS system can degrade more than 95% of 10 mg per L Rhodamine (RhB) at an initial pH of 7, which possesses higher catalytic activity than the Fe3O4/PMS system and the MIL-101(Fe, Co)/PMS system. The effects of initial solution pH and coexisting anions in water on the degradation of RhB were further discussed. The results showed that Fe3O4@MIL-101(Fe, Co) displayed excellent degradation efficiency in a wide pH range of 3–11 and capability of resisting coexisting anions. It is worth mentioning that after five cycles, the RhB removal rate can still be maintained at over 90% after 10 minutes of reaction. Free radical quenching experiments were further studied, confirming that ˙OH and SO4−˙ were involved in the degradation of RhB, while the dominating active free radical was SO4−˙. The possible reaction mechanism of the RhB degradation process was also inferred.
研究领域:
环境科学
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材料科学
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PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
·
IF 13.2
Zehua Wang,Ziyang Peng,Dan Li,Xinyi Liu,Qiong Mei,Jianfei Sun,Hongjie Wang
Thiamethoxam (THX), a neonicotinoid pesticide, exhibits potential ecotoxicity in aquatic environments. In this study, a combined experimental and density functional theory (DFT) approach was applied to investigate partial Fe-substituted Co 3 S 4 (Fe x Co, x = 0.01, 0.03, 0.05, 0.07, 0.09, and FeCo 2 S 4 ) for the effective activation of PMS and the degradation of THX. Fe doping elongated Co S bonds on the catalyst to promote the formation of sulfur vacancies, which enhance the adsorption and charge transfer capability of PMS. Due to the fastest degradation rate (0.511 min −1 ), the optimal PMS adsorption stability (1.11 eV), more electron transfer (0.72 e − ), and longer O O bond (1.468 Å), Fe 0.03 Co catalyst can preferably activate PMS to generate SO 4 •- and 1 O 2 , which was the most significant ROS for degrading THX. The initiation reaction of SO 4 •- -addition was superior to 1 O 2 , and the optimal active site was the C2 sites. Proposed degradation pathways and ecotoxicity evaluation highlighted the critical role of denitrification and hydroxylation in toxicity attenuation. In addition, Fe 0.03 Co/PMS catalyst had certain catalytic stability and reusability, and its degradation efficiency in farmland irrigation water can reach 80 %. This work not only elucidated the performance enhancement mechanism of Fe-substituted Co 3 S 4 catalyst, but also provided support for the application of sulfide-metals on advanced oxidation treatment of pesticide wastewater.
研究领域:
环境化学
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催化科学
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水污染控制
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理论计算化学
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农药环境行为
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高级氧化技术
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高影响因子
Journal of Environmental Chemical Engineering
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2025
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IF 7.2
Su Xu,YaNi Yi,HuaYing Li,WeiWei Zhang
Oxytetracycline (OTC), a persistent and poorly biodegradable antibiotic, is increasingly detected in aquatic environments, posing ecological and health risks. Herein, a defect-rich, Co-free MoS₂/PMS system enables ultrafast OTC removal, achieving >99% elimination within 5 min (k obs = 0.791 min⁻¹). The process remained highly efficient across pH 2–10 and in real waters containing natural organic matter and common inorganic ions, demonstrating strong robustness under complex water matrices. Radical-quenching and electron paramagnetic resonance (EPR) analyses confirmed that •OH was the dominant reactive oxygen species (ROS), accompanied by SO₄•⁻ and ¹O₂. X-ray photoelectron spectroscopy (XPS) evidenced Mo⁴⁺/Mo⁶⁺ redox cycling and the participation of surface sulfur species and lattice oxygen, which jointly facilitated PMS activation and ROS generation, thereby establishing a coupled radical-non-radical degradation mechanism. Liquid chromatography–mass spectrometry (LC–MS) identified sequential demethylation, deamination, and ring-opening intermediates, while QSAR-based ecotoxicity assessment indicated an overall decrease in predicted toxicity for most transformation products relative to OTC. Machine-learning analysis (XGBoost with SHAP interpretation) highlighted reaction time, PMS dose, and natural organic matter as the primary determinants of degradation efficiency. Overall, this work integrates a Co-free, light-independent MoS₂/PMS system, refined dual radical–non-radical mechanistic elucidation, comprehensive toxicity mitigation assessment and explainable machine learning, offering both mechanistic and engineering guidance for the sustainable treatment of antibiotic-contaminated wastewater.
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Journal of Environmental Chemical Engineering
·
2025
·Vol. 14
·期 1
·120795
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IF 7.2
Xiaolin Shi,Bo Xing,Guo Yang,Yi Wang,Pan Huang,Fuping Zhang,Qing Yang,Hangdao Qin,Ping Yang,Caiyi Jiang,Xingyong Liu
Polyvinylidene fluoride (PVDF) membrane filtration is extensively employed in the treatment of fluoride-containing wastewater due to low cost and operational simplicity. However, it still faces the challenges of unsatisfactory permeability and anti-pollution performance. In the present work, a novel PVDF ultrafiltration membrane modified with FeCo/BC (FeCo/BC@PVDF) that exhibits outstanding catalytic activity was fabricated via the non-solvent-induced phase separation (NIPS) method, which further enables the in-situ coupling between the as-fabricated membrane and peroxymonosulfate (PMS). The performance evaluation exhibits that the pure water flux and rejection rate of FeCo/BC@PVDF ultrafiltration membrane increased from 235.91 L⋅m −2 ⋅h −1 and 51.63 % to 445.61 L⋅m −2 ⋅h −1 and 90.71 %, and the irreversible pollution rate has decreased from 37.69 % to 17.67 % in in-situ coupling PMS systems. Meanwhile, the characterization results of XRD, FTIR, SEM, XPS and water contact angle (WCA) confirmed that the outstanding permeability and anti-pollution performance were attributed to good pore distribution, hydrophilicity and catalytic performance. In addition, the pollution model fitting, extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and heterogeneous experiments were used to further understand the anti-pollution mechanism of FeCo/BC@PVDF, and the results reveal that pollution mode of ultrafiltration membrane has changed from multiple contamination behaviors to easily rinsed cake layer contamination because of the in-situ degradation effect of SO₄⁻•, O₂⁻• and •OH on sodium p-perfluorous nonenoxybenzenesulfonate (OBS). This research provides a new idea for simultaneously improving the permeability and anti-pollution performance of PVDF ultrafiltration membranes in the field of fluorine-containing wastewater treatment.
研究领域:
环境科学与技术
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膜科学与工程
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水处理
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高级氧化技术
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材料科学
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高影响因子
Journal of Water Process Engineering
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2025
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IF 6.7
Dahua Yu,Qingdan Liao,Xitong Li,Fumin Liu,Jingxin Huang,Huilin Guan,Yizong Huang
The pore confinement environment critically restricts mass transfer efficiency in advanced oxidation process (AOPs). Hydrothermal carbons with hierarchical pore architectures significantly influence mass transfer of substances in AOPs, resulting in notable differences in performance. In this study, Fe-modified spent coffee grounds hydrothermal carbon (Fe@SCGSHC) contains Fe 2+ active sites, was synthesized using coffee grounds. We systematically compared the mass transfer and activation differences between persulfate (PMS) and hydrogen peroxide (H₂O₂) within a confinement pore environment, elucidating a micropore-mediated regulatory mechanism for performance of dual oxidizers. The diffusion constant of H₂O₂ ( K d₂ = 0.1953 mg/g·min 1/2 ) was 466 times greater than that of PMS ( K d₂ = 0.000419 mg/g·min 1/2 ). Besides, the oxidation rate constant of H₂O₂ increased from 0.026 to 8.481 (mg/L) −1 ·h −1 . 0.1 g Fe@SCGSHC achieved 100 % degradation of 5 mg/L sulfamethoxazole (SMX) within 5 min. The mechanistic study showed that the microporous structure enhances the Fe 2+ /Fe 3+ cycling within confined spaces, accelerating reaction kinetics and shifting traditional Fe-based catalysts from radical pathways (SO₄ •- , •OH) to singlet oxygen ( 1 O₂) pathways, revealing the selective advantage of micropores for H₂O₂ activation to generate 1 O₂. The stability experiments results indicated that 0.01 g Fe@SCGSHC achieved a 70.71 % removal of total organic carbon (TOC) in 5 mg/L SMX aquatic environments, exhibiting good anti-interference capability and ecological safety. In conclusion, the adoption of an appropriate pore structure can enhance the mass transfer efficiency of AOPs, leading to the effective degradation of pollutants. This study provides a scientific foundation for the preparation and modification of hydrothermal carbon and the mass transfer of substances in AOPs.
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高影响因子
Catalysts
·
2026
·Vol. 16
·期 1
·39
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IF 4
Yiqiong Yang,Xuyang Gao,Juan Han,Mingkun Cao,Li Qing,Liren Yu,Xiaodong Zhang
Metal–organic framework (MOF) materials were extensively studied in the removal of pollutants in wastewater. However, catalysts in the powder form usually suffered from the strong tendency to agglomerate and the intricate operation for recycling, which significantly limited their practical application. In comparison, monolithic catalysts with their high macroscopic operability and recoverability as well as impressive specific surface area have attracted tremendous attention in recent years. To address these issues, a monolithic Fe-based catalyst was prepared via in situ synthesis, using nickel–iron foam (NFF) as the substrate with cobalt (Co) incorporation. XPS analysis showed that Co doping enhanced the synergistic interaction among Fe, Ni, and Co, accelerating the redox cycle among species, thus improving electron transfer and laying a kinetic foundation for efficient peroxymonosulfate (PMS) activation. Quenching experiments and EPR indicated singlet oxygen (1O2) as the main reactive species; Co doping shifted the degradation pathway from radicals to non-radicals. Under optimized conditions (PMS: 0.08 mmol/L; catalyst: 1 cm2; initial Chlortetracycline (CTC): 50 mg/L), 95.7% CTC degradation was achieved within 60 min, and efficiency only dropped to 90.5% after 5 cycles. This catalyst provided theoretical and technical support for the application of monolithic MOF-derived catalysts and highly efficient PMS activators.
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Journal of Environmental Sciences
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2026
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IF 6.5
Xiaoxia Liang,Zewan Qin,Siwei Zhang,Rong Hai,Lingqing Gu,Xia Yang
30CNQDs@NMT/PMS achieved almost complete degradation of malathion within 30 min simulated sunlight irradiation. • CNQDs was integrated successfully to promote the charge separation efficiency as electron bridges and enhance the adsorption energy of PMS for activation revealed by DFT. • •OH and •SO 4 – were generated to attack the identified sites of malathion computed via Fukui function. • The intermediate products in the photocatalytic process were less toxic than malathion assessed by T.E.S.T. Malathion, an organophosphate pesticide widely used in agricultural fields across the world, has raised environmental concerns due to its persistence and toxicity. Thus, a novel photocatalyst was synthesized by integrating carbon nitrogen quantum dots (CNQDs) onto NH 2 -MIL-125(Ti) (NMT) via a solid-phase thermal polycondensation method. It was demonstrated that CNQDs served a dual function as electron bridges to facilitate charge separation and as peroxymonosulfate (PMS) adsorption activation sites substantially enhancing the photocatalytic activity, which was revealed by Density Functional Theory (DFT). Under simulated sunlight, 30CNQDs@NMT achieved nearly 100 % malathion removal within 30 min via PMS activation, exhibiting 8.1 times higher than NMT. While •OH and •SO 4 – acted as the dominant reactive species to attack the malathion sites. The toxicity of the intermediate products assessed by T.E.S.T. (Toxicity Estimation Software Tool) were much lower than malathion. Moreover, 30CNQDs@NMT performed effectively in real water matrices, demonstrating its potential for practical environmental applications. Download: Download high-res image (233KB) Download: Download full-size image
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2020
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IF 10.652
Zhiyan Huang,Pingxiao Wu,Chenhui Liu,Meiqing Chen,Shanshan Yang,Zhi Dang,Nengwu Zhu
Understanding the origin of high activity of graphene layers encapsulated Fe-N-C catalysts in Fenton-like reaction is critical, but still challenging for developing catalysts with high activity and durability. Therefore, we prepared a highly active Fe-N-C catalyst (Fe x Mn y -Fe@NCs) containing FeN 4 coordination to activate peroxymonosulfate (PMS) toward 4-aminobenzoic acid ethyl ester (ABEE) degradation, and revealed the multiple catalytic reaction sites by investigating the composition and the structure of the catalyst. The relationship between the catalytic degradation performance and multiple catalytic reaction sites was performed on the basis of both experiments and density functional theory (DFT) calculations. The catalytic performance of Fe 2 Mn 1 -Fe@NCs was found to show optimal catalytic degradation performance. Pyrrolic N served as adsorption site as well as singlet oxygen generation site to promote the catalytic degradation. Fe-pyridinic N-C acted as hydroxyl radical and sulfate radical generation site. Both singlet oxygen and superoxide radical were dominated the catalytic reaction. The insight achieved from this study may be further applied to other Fe-N-C catalysts design and further efficient organic pollution remediation.
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高影响因子
RSC Advances
·
2018
·Vol. 8
·期 8
·3934-3940
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IF 2.936
Chunyong Zhang,Wei Chen,Jiahui Xian,Degang Fu
In this work, a novel definitive screening design (DSD) was initially used to investigate the in situ chemical oxidation of acid orange-II (AO II) dye using a homogeneous cobalt-catalyzed peroxymonosulfate (Co2+/PMS) system. Experiments were performed in a batch reactor using a synthetic AO II solution containing cobalt ions, humic acid (HA) and five electrolyte salts (NaCl, NaNO3, NaHCO3, Na2SO4 and NaH2PO4). The effects of nine operating variables on AO II degradation: NaCl concentration (0–20 mM), NaH2PO4 concentration (0–20 mM), NaHCO3 concentration (0–20 mM), NaNO3 concentration (0–20 mM), Na2SO4 concentration (0–20 mM), HA concentration (0–40 mg L−1), PMS concentration (2–10 mM), AO II concentration (0–100 mg dm−3) and Co2+ concentration (0–1.36 mM), were investigated. Analysis of a DSD model revealed that only four variables were statistically significant. Besides, our results indicated that there were no significant interactive effects between the five anions employed. Thereafter, a central composite rotatable design (CCRD) was adopted to further optimize these significant variables. A CCRD model describing AO II conversion as a function of PMS concentration, NaCl concentration and Co2+ concentration was then constructed and used to explore the final optimal operating conditions. As a consequence, the combination of DSD and CCRD allowed reducing the number of experiments from over 600 to only 39. Lastly, a plausible reaction sequence concerning the oxidation of AO II in the Co2+/PMS/Cl− system was also proposed. The route of AO II oxidation involved hydroxylation and chlorination, signifying the roles of both sulfate radicals and active chlorine species.
研究领域:
环境科学
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化学工程
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2020
·
IF 10.652
Ying Cao,Wei Qiu,Yumeng Zhao,Juan Li,Jin Jiang,Yi Yang,Su-Yan Pang,Guanqi Liu
The frequent detection of chloramphenicol (CAP) in wastewater and surface water gives rise to concerns on its fatal myelosuppression and aplastic anemia. Recently, the combination of ozone and peroxymonosulfate (O 3 /PMS) has received wide attention in removing pollutants due to the multiple oxidants (i.e., O 3 , hydroxyl radicals ( OH) and sulfate radicals (SO 4 − )) existed therein. This study showed that O 3 /PMS could effectively degrade CAP under various conditions. The second-order rate constant of CAP with O 3 , OH and SO 4 − was 0.291 ± 0.005 , 2.27 ( ± 0.03 ) × 10 9 and 1.02 ± 0.02 × 10 8 M - 1 s - 1 , respectively. The degradation efficiency of CAP was significantly enhanced as PMS concentration or pH increased. Bicarbonate (HCO 3 − ) at concentration of 5 mM slightly inhibited CAP degradation at pH 7. Chloride (Cl − ) at concentration of 0.5 mM enhanced CAP removal at pH 7, while this enhancement gradually weakened as Cl − concentration further increased. The degradation efficiency of CAP first increased with increasing natural organic matter (NOM) concentrations (0.1–0.3 mg/L), while it was completely suppressed at higher NOM concentrations (0.5 mg/L). Four degradation products in total of CAP were identified in O 3 -based processes (i.e., O 3 , O 3 /TBA, O 3 /H 2 O 2 , O 3 /PMS and O 3 /PMS/ tert -butyl alcohol (TBA) systems. Besides, these transformation products by OH, SO 4 − and/or O 3 were also distinguished. Finally, the impact of O 3 /PMS pre-oxidation on the formation of dichloroacetamide (DCAcAm) from CAP during post-chlorination process was investigated. Compared with the traditional O 3 and O 3 /H 2 O 2 processes, O 3 /PMS pre-oxidation generally led to the least generation of DCAcAm under similar conditions, where SO 4 − rather than OH was conducive to relieve the formation of DCAcAm. Moreover, the presence of NOM obviously alleviated the formation of DCAcAm by O 3 /PMS pre-oxidation.
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高影响因子
CHEMOSPHERE
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2021
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IF 7.086
Xuan Chen,Jie Zhou,Hanwen Yang,Hui Wang,Huanxuan Li,Shengji Wu,Wei Yang
Refractory organic pollutant effluent has led to severe water pollution . In this study, magnetic Co–N-doped carbon hybrid catalysts (Co-NC- x ) were fabricated using a facile cation exchange combined pyrolysis and self-reduction technique to activate peroxymonosulfate (PMS) for rehabilitation of the water environment. Factors affecting the catalytic activity of the Co-NC-850 were comprehensively examined. 100% of RhB degradation efficiency within 20 min was achieved in the Co-NC-850/PMS system at the optimum conditions ( C 0 = 80 mg L −1 , catalyst loading 0.025 g L −1 , PMS concentration 0.8 mM, native pH and 25 °C). The electron paramagnetic resonance measurements and competitive quenching tests demonstrated that a sulfate radical (SO 4 • - ) and singlet oxygen ( 1 O 2 ) account for RhB degradation in the Co-NC-850/PMS system, and 1 O 2 contributed ~86.2% to RhB removal. The synergistic effect of Co 0 nanoparticles (NPs) and NC on Co-NC-850 might induce a predominant non-radical route to trigger PMS activation for RhB degradation. Direct oxidation of O 2 • - by a hydroxyl radical (•OH) might be the crucial process for forming 1 O 2 . Magnetic response and successive cycles verified that Co-NC-850 has superior separable performance and reusability. This innovative magnetic Co-NC-850 hybrid catalyst for PMS activation delivered vast potential for disintegration of refractory organic contaminants .
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PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 12.5
Junjie Cheng,Xinman Tu,Xinding Lv,Li Zhang,Xinjie Yang,Honghu Zeng,Jianping Zou
Current density modulates PMS activation pathways in the electrocatalytic membrane. • Sequential 1 O 2 , ETP, and radical oxidation achieves stepwise 4-CP degradation. • Polymerization-induced membrane fouling is suppressed during degradation. • Complete dechlorination and mineralization of 4-CP are simultaneously achieved. During peroxymonosulfate (PMS)-based advanced oxidation processes, uncontrolled generation of reactive oxygen species (ROS) causes phenolic substances to undergo polymerization reactions, which irreversibly block active sites and foul membrane catalytic systems. To address this, we develop a current-modulated pathway-switching strategy using a nitrogen-doped carbon quantum dots/g-C 3 N 4 nanosheet (NCQDs@CNNS) electrocatalytic membrane for complete dechlorination and mineralization of 4-chlorophenol (4-CP). By simply varying the applied current density (2, 0, and 8 mA cm −2 ), the peroxymonosulfate (PMS) activation pathway can be switched sequentially among singlet oxygen ( 1 O 2 ), direct electron transfer process (ETP), and free radicals (•OH and •SO 4 − ). Guided by theoretical calculations, the oxidation pathways are precisely tailored to the electronic structure of 4-CP and its intermediates, leading to a three-stage sequential degradation process: i) 1 O 2 first cleaves the aromatic ring without generating polymerizable phenoxy radicals; ii) ETP-triggered nucleophilic substitution then selectively dechlorinates the ring-opened intermediate; and iii) free radicals finally mineralize the residual chlorine-free aliphatic acids. This strategy completely avoids membrane fouling caused by polymerization reactions and can achieve a TOC removal efficiency of 99.3% and a dechlorination efficiency of 98.5% within 30 min, with an electrical energy per order (EEO) of 0.0026 kWh m −3 log −1 . This system maintains stable performance over five consecutive experimental cycles, and adapts well to various pH values, coexisting ions, natural organic substances, and actual water body substrates. This work provides a mechanistic strategy for the selective electrochemical regulation of oxidation pathways, which can simultaneously prevent fouling and thoroughly detoxify chlorophenolic wastewater. Download: Download high-res image (191KB) Download: Download full-size image
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