CHINESE CHEMICAL LETTERS
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2024
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IF 9.4
Junyi Yu,Yin Cheng,Anhong Cai,Xianfeng Huang,Qingrui Zhang
Herein, the Cu(III) synthesized from copper plating effluent was developed for the first time to evaluate the onsite degradation performance of heavy metal complexes in the wastewater, thus achieving the purpose of “treating waste with waste”. The results indicated that synthetic Cu(III) presented the excellent decomplexation performance for Cu(II)/Ni(II)-organic complexes. The removal efficiency of Cu(II)/Ni(II)-EDTA significantly increased with increasing Cu(III) dosage, and the degradation of Cu(II)/Ni(II)-EDTA by synthetic Cu(III) system displayed highly pH-dependent reactivity. The radical quencher experiments confirmed that Cu(III) direct oxidation were mainly involved in the degradation of Cu(II)-EDTA. Additionally, the continuous decarboxylation process was proven to be the main degradation pathway of Cu(II)-EDTA in Cu(III) system. The coexisting substances (SO 4 2− , Cl − and fulvic acids) showed little impacts at low level for the removal of Cu(II)/Ni(II)-EDTA, while retarded the degradation of Cu(II)-EDTA slightly at high level, which features high selective oxidation. Encouragingly, it was also effective to remove Cu(II)/Ni(II)-EDTA from in treating actual Cu/Ni-containing wastewater through synthetic Cu(III) treatment.
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 Advances
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2023
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IF 0
Hongchao Li,Na Yuan,Chuan Wang,Xiaofei Yan,Jieshu Qian
Transition metal oxides have been recognized as promising catalysts for the activation of peroxymonosulfate (PMS), while the underlying mechanism involved in the relevant processes remains obscure. Here, we identify the reactive species generated in the CuFe 2 O 4 /PMS process and illustrate their roles in the degradation of aromatic compounds with different substituent groups (i.e., phenol and benzoic acid). Experimental results showed that free radicals (i.e., sulfate radicals (SO 4 •− ) and hydroxyl radicals (HO • ), surface Cu(III) species, and singlet oxygen ( 1 O 2 ) coexist in the CuFe 2 O 4 /PMS process. The free radicals are mainly responsible for the oxidation of aromatic compounds with electron-withdrawing group (i.e., benzoic acid), while the surface Cu(III) is the major reactive species for the removal of aromatic compounds with electron-donating group (i.e., phenol). In addition, 1 O 2 plays a negligible role in the oxidation of both benzoic acid and phenol. This study enhances the fundamental understanding of the underlying mechanism involved in the transition metal oxides-catalyzed PMS activation process.
研究领域:
环境科学
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化学
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CHEMOSPHERE
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2021
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IF 7.086
Qing Zhao,Xiao Zhang,Dezhi Huang,Long Chen,Shuxin Li,Jean-Marc Chovelon,Lei Zhou,Guangli Xiu
Cu(II) is generally considered to be a poor activator for PMS decomposition, thus the potential impact of trace Cu(II) on PMS induced oxidation of typical pollutants is always overlooked. In this study, we reported that trace Cu(II) could significantly promote PMS induced degradation of four selected sulfonamide antibiotics (SAs), namely, sulfamehoxazole (SMX), sulfathiazole (STZ), sulfamerazine (SMZ), and sulfamonomethoxine (SMM). Different from conventional PMS-induced oxidation process, high-valent Cu(III) was ascertained as the primary reactive intermediate for SAs degradation, which was confirmed by raman tests and electron paramagnetic resonance (EPR). High concentrations of Cu(II) or PMS were beneficial to degradation of the selected contaminants. In PMS/Cu(II) oxidation system, all the selected SAs could undergo several different degradation pathways including continuous oxidation of aniline group, hydroxylation and S–N bond cleavage. In particular, for six-membered SAs, such as SMZ and SMM, a SO 2 extrusion pathway was also detected. The potential mechanism for Cu(III) formation was also proposed, which was believed to be highly related to the nature of the SAs. Hydroxylamine-SAs (N 4 –OH–SAs), generated from direct PMS oxidation of SAs, was deduced as the “promoter” for the whole oxidation process. And the generation of Cu(III) was likely to proceed through the interaction between PMS and Cu(I), which possibly derived from the reduction of Cu(II) by N 4 –OH–SAs. The results obtained in this study validated the contribution of Cu(III) to the elimination of pollutants and expanded our understanding of the oxidation process of PMS in the presence of trace amounts of Cu(II).
研究领域:
环境化学
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水处理
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污染物降解
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PubMed
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2020
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IF 7.864
Lihong Wang,Haodan Xu,Ning Jiang,Zimeng Wang,Jin Jiang,Tao Zhang
Activation of persulfates to degrade refractory organic pollutants is currently a hot topic of advanced oxidation. Developing simple and effective activation approaches is crucial for the practical application of persulfates. We report in this research that trace cupric species (Cu(II) in several μM) can efficiently trigger peroxymonosulfate (PMS) oxidation of various organic pollutants under slightly alkaline conditions. The intermediate oxidant dominating this process was investigated with electron paramagnetic resonance (EPR), chemical probing, and in situ Raman spectroscopy. Unlike conventional PMS activation, which generates sulfate radical, hydroxyl radical, or singlet oxygen as major oxidants, Cu(III) was confirmed to be the primary and selective intermediate oxidant during the Cu(II)/PMS oxidation. Hydroxyl radical is the secondary intermediate oxidant formed from the reaction of Cu(III) with OH–. Hybrid oxidation by the two oxidants imparts Cu(II)/PMS with high efficiency in the degradation of a series of pollutants. The results of this work suggest that, with no need of introducing complex catalysts, trace Cu(II) inherent in or artificially introduced to some water or wastewater can effectively trigger PMS oxidation of organic pollutants.
研究领域:
环境科学
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化学工程
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PubMed
高影响因子
Journal of Cleaner Production
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2020
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IF 7.246
Hongping He,Mei Sun,Deli Wu,Guanglan Di,Xunchang Fei
Heterogeneous Fenton dominated by ·OH is limited in its application, as pre-acidification is required to maximize the generation amount and redox potential of ·OH. It is thus featured to consume resources and generate pollutants. In this study, both CuS/H 2 O 2 and Cu 2 S/H 2 O 2 are found to show better performances under close-to-neutral condition (pH 5.0 to 9.0) than acidic condition (pH 3.0) when degrading a model contaminant, sulfamethazine (SMZ), because ·OH does not play a major role in both systems. The Cu valence-dependent catalytic mechanisms are responsible for the varied kinetics between CuS/H 2 O 2 and Cu 2 S/H 2 O 2 . In CuS/H 2 O 2 , Cu(III) and 1 O 2 contribute to the SMZ degradation, and their contributions are pH-dependent. In Cu 2 S/H 2 O 2 , Cu(III) is responsible for the degradation regardless of the pH. Both systems with optimal performances under neutral condition are advantageous as pre-acidification can be avoided. In addition, air sparging induces additional 16% SMZ degradation in Cu 2 S/H 2 O 2 under acidic condition, because the sparged O 2 reacts with dissolved Cu(I). The more O 2 reacts with the dissolved Cu(I), the less generated Cu(III) is ineffectively depleted. Air sparging is readily applicable to different operations, thus its combination with Cu 2 S/H 2 O 2 potentially benefits the development of environmentally-friendly treatment process for industrial wastewater .
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
Journal of Environmental Chemical Engineering
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2025
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IF 7.2
Haifeng Zhang,Ziyi Liu,Zhi Xu,Chunying Teng,Wei Chen,Lanhe Zhang,Jian Zhang
The Fenton-based oxidation process is an effective wastewater treatment approach for degrading organic pollutants. However, it has limitations in terms of pH range and secondary pollution. Cu(II)-mediated Fenton-like oxidation presents a promising alternative for applications. In this work, experimental approaches were integrated with kinetic modeling analysis to understand the production, performance and reaction mechanism of active species during the Cu(II)/H 2 O 2 process. Chemical probe analysis and electron paramagnetic resonance information verified the presence and properties of ·OH and Cu(III) in the Cu(II)/H 2 O 2 process. By using the periodate colorimetric technique, the relationship between reaction conditions and the generation of Cu(III) was further clarified. Together with theoretical analysis, the contribution of ·OH and Cu(III) to the elimination of bisphenol A (BPA) in the Cu(II)/H 2 O 2 process was examined. Quantitative analysis demonstrated that ·OH played a pivotal role under acidic conditions, accounting for 54.06 % and 62.06 % of BPA removal at pH 4 and 6, respectively. However, a dramatic shift occurred under alkaline conditions, where ·OH contributions decreased substantially to·3.35 % and 0.89 % at pH 10 and 12, respectively. The kinetic model for the removal of BPA by Cu(II)/H 2 O 2 process was calculated as V= 0.236·[BPA] 0.173 ·[Cu(II)] 0.619 ·[H 2 O 2 ] 1.556 using one-eighth lifetime method. Furthermore, Cu(III) was found to be more reactive toward the benzene ring than ·OH. This work contributes to our understanding of the Cu(II)-mediated Fenton-like oxidation process, and it could offer a promising new method for treating refractory organic wastewater.
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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2023
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IF 15.1
Ping Zhang,Mingxue Xiang,Wei Jiang,Huiling Liu,Yu Chen,Ying Fang,Longyong Wu,Hongjun Guo,Yufei Wang
Integrated adsorption and photocatalysis is a worth frontier strategy for recalcitrant organics elimination, yet the current challenge is developing materials featured with dual functions of adsorption/photocatalytic ability. In this scenario, a novel attractive exfoliated vermiculite coupling with Cu(II) composite (eVT@Cu) was tactfully engineered. Specifically, exfoliated structure containing vast negative charge was conductive for Cu(II) loading. The anchored Cu(II) played triple roles in this system, that is, regulating electron configuration of photocatalyst with narrow bandgap, as well as providing complexation sites for tetracycline (TC) enrichment. With the help of inherent Fe(III), Cu(II) was readily to form heterogeneous high-valence Cu(III) driven by photonic energy. Benefited by these effects, eVT@Cu exhibited extremely augment on TC removal compared to pristine VT and eVT, with ca. 80% removal efficiency through the synergy of adsorption and photocatalysis. Overall, this study not only provides an excellent environmental candidate for TC removal but also opens a brand-new perspective for the generation of heterogeneous high-valence Cu(III) over eVT@Cu under visible light.
研究领域:
环境科学
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材料科学
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化学工程
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高影响因子
Environmental Science-Water Research & Technology
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2024
·Vol. 10
·期 8
·1785-1794
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IF 3.5
Jun Zhang,Shenjun Wang,Yuhao Wu,Jiahai Ma
In advanced oxidation systems, the promoting effect of bicarbonate is relatively overlooked. Bicarbonate, as an inorganic anion widely present in natural waters, is extremely important for water treatment. Therefore, bicarbonate was added to a PDS/Cu2+ system to investigate the degradation mechanisms of organic contaminants. The generation of alkyl radicals in the PDS/Cu2+/HCO3− system was first demonstrated through Electron Paramagnetic Resonance (EPR) testing. This study reveals that the introduced bicarbonate ions undergo transformation into alkyl radicals. The presence of alkyl radicals promotes the cycling of monovalent, divalent, and trivalent copper ions, facilitating the degradation of contaminants. The production of monovalent and trivalent copper ions in the reaction system was confirmed through UV-vis absorption spectroscopy and quenching experiments. Furthermore, the change in the oxidation state of copper ions was further confirmed through EPR testing. These findings not only shed new light on the degradation mechanism of the PDS/Cu2+ system in the presence of bicarbonate but also open up new avenues for the further application of bicarbonate in advanced oxidation processes.
研究领域:
环境科学
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化学
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高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2024
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IF 12.2
Ziyang Chu,Zhengyan Han,Haibo Liu,Tianhu Chen,Xuehua Zou,Hanlin Wang,Fuwei Sun,Hao Wang,Dong Chen
The simultaneous removal of heavy metal complexes (HMCs) and heavy metal ions presents a significant challenge in treating wastewater. To address this, we propose a Calcite/Peroxymonosulfate (Calcite/PMS) system aimed at simultaneously decomplexing Cu-EDTA and removing Cu ions . Calcite/PMS system could achieve 99.5 % Cu-EDTA decomplexation and 61.9 % Cu ions removal within 60 min under initial conditions of Cu-EDTA (10 mg/L), Calcite (3 g/L), and PMS (2 mM). Singlet oxygen ( 1 O 2 ) emerged as the predominant reactive species responsible for Cu-EDTA decomplexation, which selectively targeted the N-C bonds in the Cu-EDTA structure to produce intermediates with lower biotoxicity than EDTA. Interestingly, solid phase Cu(III) (≡Cu(III)) promoted the generation of superoxide radicals (O 2 •− ) with a contribution of up to 72.8 %. Subsequently, nascent ≡Cu(III) and O 2 •− accelerated the degradation of intermediates. Besides, coexisting organic substances inhibited Cu-EDTA decomplexation, whereas inorganic ions had a weak impact. After five cycles of use, the Calcite/PMS system retained 99.3 % efficiency in decomplexing Cu-EDTA. This investigation provides valuable insights into using calcite to remove HMCs and enhances our comprehension of the decomplexation intermediates accelerating HMCs degradation.
研究领域:
环境科学
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化学
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PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2022
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IF 9.136
Haoran Song,Shiting Pan,Yuwei Wang,Yang Cai,Wei Zhang,Yongming Shen,Changping Li
There exists an obvious contradiction between Cu(III) generation and Cu(I) contribution in reductants enhanced Cu(II)/peroxymonosulfate (PMS) process because the involved electron transfer pathways were always ignored in previous studies. This study investigated the MXene-mediated electron transfer mechanism in Cu(II)/PMS for the first time. The introduction of MXene significantly promoted atrazine degradation under acidic condition because the in-situ generation of Cu(I) was an excellent activator for PMS. Under alkaline condition, although addition of MXene generated a large amount of Cu(I), the degradation of atrazine was inhibited due to that the conversion of Cu(I) to Cu(III) was interrupted. The strong metal-support interaction (SMSI) altered the reactive intermediate species from Cu(III) (two-electron transfer) to hydroxyl radical (HO • ) and sulfate radical (SO 4 •- ) (one-electron transfer) under alkaline condition. This work proposed a novel MXene-mediated electron transfer mechanism and improved the understanding of Cu(III)/Cu(I) transformation pathway.
研究领域:
环境科学
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材料科学
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高影响因子
WATER RESEARCH
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2022
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IF 13.4
Fuwei Sun,Tianhu Chen,Ziyang Chu,Peixun Zhai,Haibo Liu,Qiang Wang,Xuehua Zou,Dong Chen
A system of Cu 2+ /calcite/PDS was constructed to degrade sulfadiazine (SDZ). Different from the traditional Cu-mediated activation, a low concentration of Cu 2+ that met drinking water standards (≤ 1 mg/L) transformed into Cu(Ⅱ) solid in the presence of calcite, and then enhanced the degradation of SDZ via PDS activation over a pH range from 3 to 9. According to scavenger and chemical probe experiments, Cu(Ⅲ), rather than radicals (hydroxyl radicals and sulfate radicals) and singlet oxygen, was the predominant reactive species, which was responsible for the degradation of SDZ. Based on the results of XRD, ATR-FTIR, and CV curves et al., CuCO 3 was the main complex with high reactivity for PDS activation to form Cu(Ⅲ). Moreover, detailed degradation pathways of sulfadiazine were proposed according to the UPLC-ESI-MS/MS and their toxicity was predicted by ECOSAR. Besides, the real water matrix would not seriously affect the degradation of SDZ in the Cu 2+ /calcite/PDS system. In summary, this study reveals a new insight into the synergistic effect of Cu 2+ and calcite on the SDZ degradation, and promotes an understanding of the environmental benefits of natural calcite.
研究领域:
环境科学
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化学工程
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分析化学
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水处理
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DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2021
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IF 13.273
Zhi Xu,Zi-He Meng,Song-Hai Wu,Shi-Jie Wang,Peng-Yue Zhu,Yong Liu,Hai-Tao Ren,Shao-Yi Jia,Xu Han
Sulfate radical (SO 4 •− ) is always thought to be an important oxidizing species in the metal-sulfite [S(IV)] systems, however, the oxidizing species correlated with the metal species have rarely been mentioned. In this study, the oxidizing species that oxidize arsenite [As(III)] in the Cu(II)-S(IV) system were investigated under alkaline conditions. Kinetic results indicate that complexation between Cu(II) and S(IV) is the pre-requisite to initiate various oxidizing species, followed by internal electron transfer from S(IV) to Cu(II) with the formation of SO 3 •− and the Cu I (SO 3 ) n −2n+1 complexes. Quenching experiments rule out contributions of SO 5 •− , peroxymonosulfate (HSO 5 − , PMS), hydroxyl radical ( • OH), superoxide radical (O 2 •− ) and singlet oxygen ( 1 O 2 ) to As(III) oxidation in the Cu(II)-S(IV) system and indicate that some kinds of peroxo species contribute. On the other side, apart from the oxidizing species such as SO 5 •− , PMS and SO 4 •− generated via a series of reactions between SO 3 •− and O 2 , the Cu I (SO 3 ) n −2n+1 complexes also react with O 2 to form Cu II -O 2 •− -(SO 3 2− ) n superoxo species and Cu III -O 2 2− -(SO 3 2− ) n peroxo species, as revealed by Raman analysis. UV–vis spectrum further confirms the presence of Cu(III) in the Cu(II)-S(IV) system. We therefore suggest that both SO 4 •− and the Cu(III)-peroxo species play important roles in the oxidation of As(III) in the Cu(II)-S(IV) system. This study enriches our understanding on the diversity of oxidizing species in the metal-S(IV) systems under alkaline conditions.
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高影响因子
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