JOURNAL OF HAZARDOUS MATERIALS
·
2022
·
IF 14.224
Shiwei Xie,Chang Li,Hui Zhan,Wei Shao,Yuanxin Zhao,Peng Liu,Peng Liao
Fe-based replacement and precipitation are promising methods for removal of copper ethylenediaminetetraacetic acid (Cu(II)-EDTA) but are limited by the necessity of controlling pH and dissolved oxygen. The details of the decomplexation mechanism also remain unclear. The present work investigated an anoxic iron electrocoagulation process capable of automatically modulating anoxic conditions and solution pH during exposure to air and thus promoting the rapid and thorough decomplexation of Cu(II)-EDTA. Dissolved Fe (II), rather than Fe(II)-bearing minerals, was found to be primarily responsible for the reduction of Cu(II)-EDTA to Cu(I)-EDTA and for the subsequent replacement reaction to generate free Cu(I) ions within the initial pH range of 2–7. The Cu(I) was primarily precipitated as Cu 2 O on the surface of green rust and magnetite as the pH was increased. The aeration of these Fe-containing precipitates released free Cu(I) ions instead of chelated Cu into solution, allowing for recycling of the Cu. This release of Cu(I) was likely induced by the pH decrease during aeration. This study provides important insights regarding the reductive decomplexation of chelated Cu(II) and the recovery of Cu via anoxic iron electrocoagulation, which is a promising green approach to recycling Cu from wastewater.
研究领域:
环境科学
·
废水处理
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高影响因子
Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Jinghui Wang,Chengyu Wang,Yuhang Zhang,Zhijun Luo,Lingling Qu
A heat-activated sodium percarbonate and persulfate (heat-SPC-PS) system was employed to treat Cu(II)-EDTA wastewater effectively. In this binary-oxidant system, SPC functioned as an oxidant, precipitant, and neutralizer throughout the treatment process. Under optimized conditions (SPC dosage: 28.3 mM, PS dosage: 47.0 mM, temperature: 80 °C), the system achieved a Cu removal efficiency of 95.9 % and rate constant of 0.391 min −1 after 10 minutes of treating a 3.14 mM of Cu(II)-EDTA solution. The Cu ions released from Cu(II)-EDTA were precipitated as a mixture of CuO, CuCO₃, and Cu₂(OH)₂CO₃. Additionally, SPC neutralized the H⁺ ions generated from PS hydrolysis, yielding a final solution pH of approximately 7.86. When followed by an alkali precipitation (AP) step at pH 11, the combined heat-SPC-PS + AP process further increased Cu removal efficiency from 95.9 % to 98.4 %, with precipitation occurring as CuO. Reactive oxygen species (ROS) generated by heat-SPC-PS system, including OH • , SO 4 •- , O 2 •- , and 1 O 2 were key contributors to the decomplexation of Cu(II)-EDTA. Moreover, the treatment substantially reduced phytotoxicity of Cu(II)-EDTA solutions. Lettuce grown with the treated effluent exhibited growth indices comparable to those irrigated with deionized water, demonstrating the potential of the heat-SPC-PS system for the safe and effective treatment of heavy metal complexes in wastewater.
研究领域:
环境科学
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化学工程
·
生物学
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高影响因子
WATER RESEARCH
·
2026
·
IF 12.8
Yifei Peng,Ruya Chen,Zhuoya Fang,Xinyuan Qiu,Qingzhen Wang,Huajun Feng,Jinming Luo,Yijing Xia
Sulfur-mediated electroreduction provides an attractive route for the concurrent decomplexation and recovery of persistent Cu(II)-EDTA; however, the intrinsic activity of sulfur sites remains poorly defined. Here, MoS 2 is employed as a model platform to delineate the role of sulfur functionalities by comparing the metallic 1T and semiconducting 2H phases. Studies reveal that sulfur sites promote a direct two-electron reduction pathway from Cu(II) to Cu(0). In the 1T phase, enhanced covalent Cu-S interactions lower the adsorption and activation barriers of Cu(II)-EDTA, while the elevated density of states at the Fermi level facilitates rapid electron transfer. Combined spectroscopic and theoretical analyses further show that sulfur vacancies and distorted octahedral coordination in 1T-MoS 2 modulate the electronic structure of sulfur sites, thereby promoting Cu extraction and lowering the decomplexation barrier. Consequently, 1T-MoS 2 achieves 99.4% Cu recovery with > 99% EDTA preservation, corresponding to an energy efficiency of 198.80 g kWh -1 (at an initial concentration of 100 mg L -1 ), outperforming 2H-MoS 2 (82.85%, 153.43 g kWh -1 ). This sulfur-mediated pathway concurrently enables stable operation over 30 cycles with high selectivity in complex matrices. Moreover, the strategy extends to other metal-EDTA systems ( e.g. , Pb(II), Cd(II)), highlighting the generality of sulfur-active electrocatalysts for coupling ligand preservation with efficient heavy-metal recovery.
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高影响因子
ELECTROCHIMICA ACTA
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2018
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IF 5.116
Yue Song,Tianran Sun,Long Cang,Song Wu,Dongmei Zhou
Further research into more cost-effective methods to treat toxic metal-ethylenediaminetetraacetate (Me-EDTA) complexes is required due to their high bioavailability. In this study, we compared electrodialysis (ED) with different compartment designs (2-, 3- and 4-compartment designs) and electrochemical oxidation (EO, 1-compartment design) to treat a dilute Cu(II)-EDTA solution (1 mM). After a 48-h treatment with a constant current applied at 32 mA, the Cu removal efficiencies were achieved at 49%, 87%, 79% and 96% for 1-compartment EO and 2- to 4-compartment ED, respectively, and the total organic carbon concentrations decreased from 138 mg/L to 100, 64, 57 and 39 mg/L, respectively. The energy consumptions for 1-compartment EO and 2- to 4-compartment ED were 7.7, 8.4, 13.9 and 15.4 W h, respectively. Based on all above results, the most cost-effective design was determined to be the 2-compartment ED. Moreover, the 3- and 4-compartment ED treatments have faster contaminant removal kinetics than 1-compartment EO and 2-compartment ED. This study clarified the mechanisms of the migration and the transformation of Cu-EDTA during EO and ED with different membrane combinations, which is helpful for improved selection of compartment design for metal-chelate complex removal.
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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2026
·Vol. 14
·期 3
·123082
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IF 7.5
Zhe Xu,Jiantong Zhou,Chengfeng Liu,Weilan Zhen,Taicheng An
The peroxodisulfate (PDS)-based oxidation systems are promising for Cu(II) complex decomplexation owing to its capacity to harness the self-enhanced decomplexation (SED) effect of Cu(II) complexes. This phenomenon was conventionally attributed to liquid-phase autocatalysis via Fenton-like reactions between daughter Cu(II) species and PDS. However, this frequently adopted hypothesis is inconsistent with the actual catalytic activity of Cu(II) species and has been challenged by our preliminary results. Herein, we revisit the decomplexation of copper(II)-ethylenediaminetetraacetate (Cu(II)-EDTA) in UV/PDS system, with particular emphasis on correcting the catalytic behaviors of Cu species and clarifying the indispensable role of UV-irradiation in SED effect. Both acidic and alkaline conditions exhibit significant SED effect, but we reveal a pH-dependent SED mechanism that is fundamentally different from the prevailing liquid-phase autocatalysis mechanism. Under acidic conditions, Cu(II) complexes exhibit enhanced catalytic capacity with decreasing ligand coordination strength, primarily stemming from the activation of PDS by Cu(I) species produced via the irradiation-induced intramolecular charge transfer; In alkaline environments, only liberated Cu(II) substantially contribute to SED effect via spontaneous hydrolysis, forming nanostructured CuO after aging, which activates PDS through heterogeneous Fenton-like processes. While acidic conditions demonstrate faster decomplexation, alkaline-generated solid products facilitate multi-cycle treatment efficiency and alkaline conditions also exhibits stronger resistance to chloride. This work corrects the misinterpretation of SED mechanism in UV/PDS/Cu(II)-EDTA system, and provides a fundamental and accurate mechanistic basis for the efficient treatment of copper-containing organic wastewater by PDS-based processes.
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CHEMICAL ENGINEERING JOURNAL
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2019
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IF 8.355
Zhe Xu,Tiancheng Wu,Yu Cao,Congcong Chen,Shanming Ke,Xierong Zeng,Peng Lin
A promising strategy to treat wastewater containing heavy metal complexes (HMCs) is to employ oxidation processes before carrying out the conventional processes. Metal ion-catalyzed oxidation processes (MICOPs) have been confirmed to be suitable for the remediation of wastewater. However, the treatment of HMCs by MICOPs has seldom attracted researchers’ attention and the key mechanisms remain unclear. In this study, Cu II -ethylenediamine tetraacetic acid (EDTA) was used to evaluate the decomplexation efficiency of various MICOPs, among which the Co II /peroxymonosulfate (PMS) system provided the best results. In-depth analysis of the decomplexation mechanism of Cu II -EDTA indicated that the high affinity of Cu(II) to EDTA inhibits the exchange between Co II and Cu II in Cu II -EDTA, thus preventing the chelation of the catalytically active Co 2+ with EDTA, which leads to the rapid decomplexation of Cu II -EDTA. Moreover, through thermodynamic computation, Mn II -EDTA, Cd II -EDTA, and Ni II -EDTA were selected as other HMC candidates to investigate their influence on the oxidation efficiency of the Co II /PMS system. The results confirmed that the oxidation efficiency of Co II /PMS is strongly dependent on the metal-ion replacement. Finally, we propose that the distinct performance of the Fenton(-like) process in decomplexing the Ni II -EDTA and Cu II -EDTA could be well explained by the metal-ion replacement mechanism.
研究领域:
环境科学
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化学工程
·
水处理
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高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2020
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IF 9.038
Shiwei Xie,Wei Shao,Hui Zhan,Zheng Wang,Chengcheng Ge,Qingjie Li,Wenjing Fu
The widely usage of ethylenediaminetetraacetic acid (EDTA) arises environmental concerns on toxic metal mobilization, and challenges the conventional processes in water treatment. In the study Cu(II)-EDTA in near natural water was efficiently removed during a two-step electrocoagulation using Fe(0) anode (Fe-EC), including a transformation to Fe(III)-EDTA induced mainly by structural Fe(II) in anoxic Fe-EC and further degradation in oxic Fe-EC. The degradation of Fe(III)-EDTA was mostly attributed to an oxygen activation mechanism that involving O 2 − and hydroxyl radical ( OH) generation, as validated by the quenching experiments and electron spin resonance. Furthermore, O 2 − generated during Fe(II) oxidation took a dominant role on Fe(III)/Fe(II)-EDTA transformation instead of electrochemical reduction. Six intermediates during the Fe(III)-EDTA degradation were identified by LC-Q-TOF, indicating a pathway of stepwise breakage of N C bonds. The results revealed in this work is helpful to understand the contribution and fate of EDTA during Fe-EC treatment of metal-EDTA polluted water.
研究领域:
环境科学
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水处理
·
化学工程
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高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2023
·
IF 13.6
Yuhang Zhang,Donglei Li,Liang She,Furong Guo,Falong Jia,Lizhi Zhang,Zhihui Ai,Xiao Liu
Heavy metal complexes in industrial wastewater are challenging to be removed by conventional methods arising from their stable chelating structure. In this study, zero-valent iron (ZVI) was ball-milled with tiny formic acid (FA), and the as-prepared sample (FA-ZVI bm ) was attempted to eliminate a model heavy metal complex of Cu(II)-ethylenediaminetetraacetic acid (Cu(II)-EDTA). The addition of FA to ball-milling could dramatically enhance the performance of ball-milled ZVI (ZVI bm ) towards Cu(II)-EDTA removal and increase the removal rate constant by 80 times. This conspicuous improvement of Cu(II)-EDTA elimination was attributed to the ferrous formate (Fe(HCOO) 2 ) shell formed on the surface of FA-ZVI bm . Results revealed that the Fe(HCOO) 2 shell facilitated the activation of O 2 to reactive oxygen species (ROS) and the leaching of Fe 3+ . Cu(II)-EDTA was decomplexed through both oxidative destruction and Fe 3+ replacement, and the released Cu 2+ was reduced by FA-ZVI bm and immobilized synchronously. Meanwhile, the ligands underwent oxidative degradation by ROS, thus avoiding the re-chelation ecological risk. Impressively, FA-ZVI bm could achieve cyclic treatment of actual copper complex wastewater and possessed promising advantage in treatment cost. This study would offer a promising approach for eliminating Cu(II)-EDTA through EDTA ligands degradation and synchronous Cu(II) removal, moreover to shed light on the decomplexation mechanism.
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