JOURNAL OF HAZARDOUS MATERIALS
·
2021
·
IF 10.588
Heng Zhang,Mengfan Luo,Peng Zhou,Yang Liu,Ye Du,Chuanshu He,Gang Yao,Bo Lai
Recently, the enhancing role of hydrogen peroxide (H 2 O 2 ), a self-decay product of ferrate (Fe(VI)), on Fe(VI) reactivity has received increasing attention. In this study, we found that calcium peroxide (CaO 2 ) as a slow-releasing reagent of H 2 O 2 could also enhance the Fe(VI) performance for removing sulfamethoxazole (SMX). Compared with sole Fe(VI), sole CaO 2 and Fe(VI)-H 2 O 2 systems, the Fe(VI)-CaO 2 system showed higher reactivity to remove SMX. The radical scavenger and chemical probe test results indicated that the better oxidation performance of Fe(VI)-CaO 2 system than Fe(VI) alone was ascribed to the generation of Fe(Ⅳ) and Fe(Ⅴ) rather than • OH. In addition, the performance of Fe(VI)-CaO 2 system for degradation of contaminants was also superior to Fe(VI)-Na 2 SO 3 , Fe(VI)-NaHSO 3 and Fe(VI)-Na 2 S 2 O 3 systems under the same experimental conditions. Moreover, the effects of critical operating parameters, inorganic anions, inorganic cations, and humic acid on the degradation of SMX by Fe(VI)-CaO 2 system were revealed. The Fe(VI)-CaO 2 system exhibited good applicability in authentic water. Finally, the underlying degradation intermediates of SMX by Fe(VI)-CaO 2 system and their toxicity were confirmed. In conclusion, this study provides a new strategy for enhancing the oxidation capacity of Fe(VI) and comprehensively reveals the oxidation mechanism.
研究领域:
环境科学
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水处理技术
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
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IF 13.3
Jialong Yin,Heng Zhang,Mengfan Luo,Jia Zhao,Bingkun Huang,Pinji Chen,Zhenpeng Cai,Yue Yuan,Yang Liu,Chuanshu He,Bo Lai
The ferrous species (Fe(II))-periodate (PI) system employs efficient decontamination by generating ferryl species (Fe(IV)-oxo) under acidic pH conditions. However, the mechanisms by which the Fe(II)/PI system operates across a broad pH range remain elusive. In light of the rapid oxidation and consumption of Fe(II) at neutral pH, we developed an electro-Fe(II) system utilizing an iron plate anode to activate PI (E(Fe/C)/PI). Efficient sulfamethoxazole (SMX) degradation was achieved under the E(Fe/C)/PI system across a range of pH values. Quenching and chemical probe experiments revealed a transition from Fe(IV)-oxo to singlet oxygen ( 1 O 2 ) as the predominant reactive species from acidic to near-neutral pH, respectively. Density functional theory (DFT) calculations indicated that the differences in one-electron transfer capacity and hydrolysis pathways for various protonated Fe(IV)-oxo species underlie the variations in catalytic mechanisms. This study not only enhances the efficiency of the Fe(II)/PI system but also provides a comprehensive understanding of the activation mechanisms at different pH levels.
研究领域:
环境化学
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电化学
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催化
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水处理
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DOI
高影响因子
WATER RESEARCH
·
2022
·
IF 13.4
Haolin Xu,Rundong Chen,Sheng Liang,Zhenchao Lei,Wenxiao Zheng,Zhang Yan,Jianxin Cao,Chaohai Wei,Chunhua Feng
The formation of chlorinated byproducts represents a significant threat to the quality of the effluent treated using electrochemical advanced oxidation processes (EAOPs), thus spurring investigation into alleviating their production. This study presents a new strategy to minimize the release of chlorinated intermediates during the electrochemical oxidation of Ni-EDTA by establishing a dual mixed metal oxide (MMO)/Fe anode system. The results indicate that the dual-anode system achieved a substantially higher rate (0.141 min − 1 ) of Ni-EDTA destruction and accordingly allowed a more pronounced removal of aqueous Ni (from 39.85 to 0.63 mg L − 1 ) after alkaline precipitation, compared with its single MMO anode (0.017 min − 1 of Ni-EDTA removal, with 14.38 mg L − 1 Ni remaining) and single Fe anode (insignificant Ni-EDTA removal, with 38.37 mg L − 1 Ni remaining) counterparts. Compared to reactive chlorine species (RCS) produced from the single MMO anode system, Fe(IV) was in situ generated from the dual-anode system and was predominantly responsible for the attenuation of chlorinated byproducts and thus the decrease in the acute toxicity of the treated solution (evaluated using luminescent bacteria). The Fe(IV)-dominated dual-anode system also exhibited superior performance in removing multiple pollutants (including organic ligands, Ni, and phosphite) in the real electroless plating effluent. The findings suggest that the strategy for Fe(II) transition to Fe(IV) by active chlorine paves a new avenue for yielding less chlorinated products with lower toxicity when EAOPs are used to treat chloride-containing organic wastewater.
研究领域:
环境科学
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电化学工程
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产品关联
DOI
PubMed
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2024
·
IF 10.8
Guang Li,Yiqiao Zhang,Xue Zhang,Jian Zhang,Bo Sun
This study delves into the formation of ferryl ions (Fe(IV)) within the Fe(II)/peroxydisulfate (PDS) process, a pivotal reaction in advanced oxidation processes (AOPs) aimed at organic pollutant removal. Our findings challenge the conventional view that Fe(IV) predominantly forms through oxygen transfer from PDS to Fe(II), revealing that sulfate radicals (SO4•–) play a crucial role in Fe(IV) generation. By employing competitive kinetics, the second-order rate constant for Fe(III) oxidation by SO4•– was quantified as 4.58 × 108 M–1 s–1. Factors such as the probe compound concentration, chloride presence, and iron species influence Fe(IV) generation, all of which were systematically evaluated. Additionally, the study explores Fe(IV) formation in various Fe(II)-activated AOPs, demonstrating that precursors like peroxymonosulfate and H2O2 can also directly oxidize Fe(II) to Fe(IV). Through experimental data, kinetic modeling, and oxygen-18 labeling experiments, this research offers a comprehensive understanding of the Fe(II)/PDS system, facilitating the optimization of AOPs for pollutant degradation. Finally, introducing HSO3– was proposed to shift the Fe(II)/PDS process from Fe(IV)-dominated to SO4•–-dominated mechanisms, thereby enhancing pollutant removal efficiencies.
研究领域:
环境科学
·
化学动力学
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Huimin Hu,Qiwu Zhang,Chao Wang,Min Chen,Qian Wang
Soluble Fe(IV) has been proposed as primary reactive species in advanced oxidation technology, however, Fe(IV) in solid-state oxidant is rarely reported. This study reports a facile synthesis of CaMn 1-x Fe x O 3 (0.1 ≤ x ≤ 0.7) containing high ratio of Fe(IV) by low-temperature calcination of the ball milling precursor and evaluates its adsorption-oxidation performances of As(III). Although Fe(IV) and Mn(IV) inside CaMn 1-x Fe x O 3 both act as electron acceptor species, with × for Fe ratio increased, charge transport capability and oxidation performance of As(III) to As(V) of the CaMn 1-x Fe x O 3 materials can be raised dramatically with more iron incorporated. With sample CaMn 0.3 Fe 0.7 O 3 , the maximal adsorption capacity for As(III) reaches 120.78 mg/g with the ratio of oxidized As(V) as high as 86.4% in a wide pH range of 2 ∼ 10. More importantly, excellent cyclability and stability are observed and 83% of the initial adsorption-oxidation capacity still retains even after 5 cycles, and leaching concentrations of the metal ions (Fe/Mn) are far below the emission standard (0.5 mg/L). With an aid of environment-friendly ball milling process, the idea to obtain high valent Fe by a simple incorporation into a specific crystalline structure of perovskite offers a new approach for synthesizing active oxidizing species of Fe(IV). Further, the synthesis of solid oxidants would transform the redox reactions from a liquid phase reaction process to a solid–liquid reaction process, which could be conducive to the occurrence of in-situ oxidation and fixation of pollutants to reduce their mobility, and much contribution is expected to the development of advanced oxidization process in wastewater treatment using the easy handling solid-state oxidants.
研究领域:
环境科学
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材料科学
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DOI
高影响因子
WATER RESEARCH
·
2022
·
IF 13.4
Zhen Wang,Yangyi Yu,Qin Guo,Chaoting Guan,Jin Jiang
Multiple reactive intermediates have been proposed to be involved in peroxydisulfate (PDS) activation by zerovalent iron (ZVI), including sulfate radical (SO 4 ·− ) produced via iron-oxide shell mediated electron transfer, ferryl ion species (Fe(IV)) formed from Fe(II)-PDS interaction, and hydroxyl radical ( · OH) generated by ZVI aerobic oxygenation. In this study, evolution of the relative role of these intermediates in microscale and nanoscale ZVI (mZVI vs. nZVI) activated PDS processes is comparatively investigated by using a methyl phenyl sulfoxide (PMSO) probe that selectively reacts with Fe(IV) to produce methyl phenyl sulfone (PMSO 2 ). Interestingly, during PMSO transformation by mZVI/PDS process, yields of PMSO 2 (η(PMSO 2 )) exhibit three-stage behavior that they first increase to a maximum (∼80% but lower than 100%) (Stage I) and then plateau for a period (Stage II) followed by a decrease phase (Stage III). Accordingly, the relative role of Fe(IV) in PMSO transformation is unceasingly improved in Stage I and subsequently reaches equilibrium with that of free radicals in Stage II, while it finally decreases in Stage III. Similar η(PMSO 2 ) evolution trends are obtained in nZVI/PDS process, except that the η(PMSO 2 ) increase in Stage I is negligible, possibly due to the exceptional fast nZVI dissolution. It was further clarified by tert -butyl alcohol scavenging assay that, in addition to Fe(IV), the free radical involved in Stages I and II is SO 4 ·− , while · OH was dominant in Stage III. Moreover, studies on O 2 effect reveal that ZVI aerobic oxygenation participates in mZVI corrosion during the entire process, while it is only involved in nZVI corrosion when PDS content is reduced to a low concentration, indicating that the reactivities of PDS and O 2 are similar in mZVI corrosion, but differ greatly in nZVI corrosion. Additionally, effects of reactant dose and pH on η(PMSO 2 ) evolution are also explored. Dynamics of the relative role of different reactive oxidants should be taken into account in further applications of ZVI/PDS in situ chemical remediation technology considering their different chemistries.
研究领域:
环境科学
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化学工程
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水处理
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Ting Zhou,Wenyi Dong,Xuechuan Li,Weigang Liu,Mengke Qiang,Hongjie Wang
High-valent ferric oxide species (HV-Fe(IV)) has been increasingly explored to selectively and efficiently remove pollutants from wastewater owing to its high reduction potential, long lifetime, and valuable resistance to anions. However, the directional production of HV-Fe(IV) and its mechanism remain challenging. Herein, a biochar-based catalyst with monoatomic Fe-trans-N 2 O 2 configuration and rich COOH group (SAFe-NKBC) was rationally constructed via KOH and supramolecular organic framework co-pyrolysis. As a result, the SAFe-NKBC/PMS system exhibited exceptional catalytic performance, achieving rapid sulfamethoxazole degradation (97.4% within 10 min) and TOC removal (73.1%). Mechanistic investigations revealed the cooperative catalytic role of single-atom Fe-trans-N 2 O 2 and COOH in biochar support via surface-confinement effect in boosting peroxymonosulfate activation and directional HV-Fe(IV) generation, mediating spatially coupled electron transfer and promoting selective oxidation pathways. Furthermore, a structure–activity relationship for various para-substituted anilines was systematically established via quantitative structure–activity relationship modeling based on different adsorption and oxidation descriptors. The valid descriptors were confirmed to predict reactivity, offering a molecular-level framework for water purification. Meanwhile, the catalyst demonstrated excellent resistance to matrix interference, long-term stability in flow-through systems, and significantly reduced toxicity of degradation byproducts, underscoring its potential in sustainable and precision-oriented water remediation. This work offered new insights into rational SAC design and reactivity prediction for sustainable water remediation.
研究领域:
环境科学
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催化化学
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水处理技术
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材料科学
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化学工程
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环境修复
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产品关联
DOI
高影响因子
Journal of Water Process Engineering
·
2025
·
IF 6.7
Yiyang Lin,Tao Lin,Han Chen,Junding Yin
The effect of N , N -bis(carboxymethyl)glutamic acid (GLDA) on the removal of organic pollutants by Fe(II)-mediated periodate (PI) advanced oxidation process at neutral pH was investigated, in which N-(1,3-dimethylbutyl)- N ′-phenyl- p -phenylenediamine quinone (6PPD-Q) was used as the model pollutant. The results showed that the Fe(II)-GLDA complex formed by mixing GLDA with Fe(II) in a 1:1 ratio reacted with PI can degrade 6PPD-Q effectively. The presence of GLDA alters the redox potential of Fe(II)/Fe(III), which allows for a better utilization of Fe(II) under the synergistic effect of ultraviolet (UV) irradiation. Based on quenching experiments, sulfoxide probe transformation and electron spin resonance (ESR) signals, the reactive species that play a major role in this process are Fe IV O and IO 3 . The degradation products of 6PPD-Q were detected by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry (UPLC-MS/MS) and two possible degradation pathways were proposed based on density functional theory (DFT) calculations. The toxicity of 6PPD-Q was found to be effectively reduced after degradation by Ecological Structure Activity Relationships (ECOSAR) software analysis and zebrafish experiments. This study provides some fundamental insights for the removal of organic pollutants by GLDA-enhanced Fe(II)/PI system under neutral conditions.
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DOI
高影响因子
CATALYSIS LETTERS
·
2025
·Vol. 155
·期 7
·1-12
·
IF 2.4
An Li-Da,Li Feng,Qiu Yi-Feng,Liang Guo-Chao,Zhang Hao,Liu Hai Yang
Comprehending how substituent effect influences catalytic performance is essential for advancing efficient catalysts and unraveling reaction mechanisms. Examining the substituent effects of metal corrole catalyzed Baeyer–Villiger (B–V) oxidation reaction remains limited. In this work, four iron tri-aryl corrole complexes with distinct electronic structures, iron(IV) 5,10,15-tris(pentafluorophenyl) corrole [Fe IV (TPFC)Cl] ( 1 a), iron(IV) 5,15-bis(pentafluorophenyl)-10-phenyl corrole [Fe IV (BPFPC)Cl] ( 2 a), iron(IV) 5,15-bis(phenyl)-10-pentafluorophenyl corrole [Fe IV (BPPFC)Cl] ( 3 a) and iron(IV) 5,10,15-tris(phenyl) corrole [Fe IV (TPC)Cl] ( 4 a) have been prepared. The impact of electron-withdrawing meso-substituents on their catalytic performance in B-V oxidation reaction was then investigated. The results reveal that an increased number of pentafluorophenyl substituents, which enhance the electron-withdrawing effect, correlates with superior catalytic activity. The catalytic activity follows an order 1 a > 2 a > 3 a > 4 a. The plausible mechanism to explain the observed catalytic behavior was also discussed. Graphical
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DOI
高影响因子
Asian Journal of Organic Chemistry
·
2025
·
IF 2.7
Yi-Feng Qiu,Xu-You Cao,Feng Li,Guo-Chao Liang,Hao Zhang,Fu-Rong Wang,Hai Yang Liu
A series of new hangman iron corroles with different electronic structure and pending aldehyde group were prepared and used as catalyst in Baeyer–Villiger (B–V) oxidation reactions. The results show that hangman iron corroles exhibit faster reaction rates and higher ε-caprolactone yields as compared to triaryl iron 5,10,15-tri(pentafluorophenyl) corrole (Fe(tpfc)Cl). With the increase in the electron-withdrawing ability of the meso-position substituents of hangman iron corrole, the yield of caprolactone also increases. Under optimal conditions, the best hangman iron corrole bearing two pentafluorophenyl groups (FePXC) may give a yield of 97% at only 0.07 mol% catalyst loading. The turnover number (TON) of the FePXC catalyst could be up to 2100 in a gram-scale test of oxidation of cyclohexanone. This work demonstrates the good potential of hangman corroles in B–V oxidation.
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Sheng Liang,Jinling Wang,Zhizhi Shen,Wei Yan,Lichao Nengzi,Chunhua Feng,Xin Lei,Li Yu,Junqing Hu
The strategy to mineralize dissolved organics for the decontamination of landfill leachate concentrate (LLC) is expensive. Because mineralization requires high stoichiometric ratio of oxidants (e.g., •OH) or electron transfer (i.e., energy) to the pollutant molecules. Whereas, transferring the dissolved organic pollutants into separable insoluble matters is an energy-saving strategy. Herein, we developed a dual-anode Fe 2+ /HClO system for removing dissolved organic pollutants in LLC through insolubilization based on oxidative coupling. In this system, the majority of dissolved organic pollutants were transferred into insoluble substances, which could be removed easily. As a result, 89.8 % of the dissolved organic carbon (DOC) in LLC was fast removed in 3 h with a low specific energy consumption (SEC, 4.0 kWh kg −1 COD and 17.6 kWh kg −1 DOC), and the formation of toxic by-products can be well controlled to total organic chlorine (TOCl) < 0.1 mg/L. The formation of insoluble substances was attributed to the oxidative coupling of organic small molecules into the macromolecular ones. This was evidenced by the generation of insoluble compounds with the larger molecular mass, and the formation of coupling or polymerization products of the model pollutant (guaiacol). The predominant mechanism was proposed that Fe(IV) was generated in the dual-anode Fe 2+ /HClO system, and Fe(IV) oxidized pollutants to produce organic radicals, then the organic radicals coupled and polymerized to form larger molecules and insoluble compounds. This work offers a novel electrochemical method for efficient removal of organic pollutants in LLC with minimal toxic by-products generated, and revealed the significance of oxidative coupling process in the electrochemical Fe 2+ /HClO system.
研究领域:
环境科学
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电化学工程
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产品关联
DOI
高影响因子
ACS Earth and Space Chemistry
·
2023
·
IF 3.4
Hao Tian,Xue-Bin Zhang,Yin-Ping Li,Qing He,Na-Na Tian,Song-Hai Wu,Xu Han
Although inorganic Fe(IV)═O oxo and Fe(III)-OOH peroxo have attracted more attention in aqueous environments, direct evidence for the characterization and identification of those oxidizing species is still lacking. In this study, the doped Cu/Co increases the reactivity of ferrihydrite/hematite in oxidizing As(III) by S(IV)-O2 under alkaline and dark conditions. Quenching experiments exclude the contributions of ·OH, O2•–, SO3•–, SO4•–, SO5•–, HSO5–, and H2O2 and confirm that peroxo and oxo are primary oxidizing species in As(III) oxidation. Electrochemical analyses indicate that Fe(IV)═O oxo and Fe(III)-OOH peroxo are primarily located on the surface of ferrihydrite and hematite. Selective oxidation of methyl phenyl sulfoxide and methyl phenyl sulfide to the corresponding oxidation products further reveals the presence of ≡Fe(IV)═O oxo on both ferrihydrite and hematite, and the doped Cu/Co significantly decreases the produced ≡Fe(IV)═O oxo on ferrihydrite, while increases the produced ≡Fe(IV)═O oxo on hematite. Meanwhile, selective oxidation of benzyl alcohol to benzaldehyde indicates the presence of ≡Fe(III)-OOH peroxo on both ferrihydrite and hematite, and the doped Cu/Co apparently increases the produced ≡Fe(III)-OOH peroxo on ferrihydrite and hematite. Raman analysis further reveals the presence of ≡Fe(IV)═O oxo and ≡Fe(III)-OOH peroxo on pure and metal-doped ferrihydrite/hematite, which also confirms that the doped Cu/Co decreases the produced ≡Fe(IV)═O oxo on ferrihydrite and increases ≡Fe(IV)═O oxo on hematite, while apparently increasing ≡Fe(III)-OOH peroxo on both ferrihydrite and hematite. This study enriches our understanding on the oxidizing species in the S(IV)-mediated oxidation processes under alkaline conditions, providing new insight on the oxidation reactivity of surface peroxo and oxo species mediated by the doped metal ions.
研究领域:
环境科学
·
化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）