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
✓ 已验证
产品关联
DOI
PubMed
高影响因子
WATER RESEARCH
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2019
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IF 7.913
Wei Xiang,Tao Zhou,Yifan Wang,Mingjie Huang,Xiaohui Wu,Juan Mao,Xiejuan Lu,Beiping Zhang
This study has demonstrated that hydroxylamine (HA) could greatly enhance Cu nanoparticles (nCu) in activating molecular oxygen and significantly elevate the diclofenac (DCF) degradation rate about two orders of magnitude in neutral circumstances. Effects of several important parameters on the DCF degradation such as nCu loading, HA dosage, pH and reaction temperature were investigated in the nCu/HA/O 2 system. Multiple examinations revealed that the reactive Cu(III) species instead of OH• would be predominant in the nCu/HA/O 2 system, despite their similar DCF degradation pathways. Based on a HA-enhanced copper cycle depending on the pristine Cu 0 @Cu(I) (hydro)oxides core-shell structure, the heterogeneous-homogeneous reaction mechanism was proposed. It included solid-liquid interfacial and bulk reactions, e.g. heterogeneous activation of O 2 by Cu(I) to produce H 2 O 2 and homogeneous Cu(I)-catalytic generation of Cu(III) from H 2 O 2 . Further quantitative investigation of the main reactive species in the cycle revealed that the Cu(I) regeneration instead of the O 2 activation would be rate-limited. Besides, nCu could be recycled to effectively degrade DCF in four consecutive cycles in the raw neural nCu/HA/O 2 system. It suggested that the nCu/HA/O 2 system with a more efficient copper cycle would be a good alternative Fenton-like system in treating neutral recalcitrant organic wastewaters.
研究领域:
环境科学
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化学工程
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF ENVIRONMENTAL MANAGEMENT
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2024
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IF 8
Tianhong Wang,Hui Zhang,Anhong Cai,Hongjie Sun,Xianfeng Huang
High valent metal species, including Mn(III), Fe(IV) and Cu(III), have been identified as key intermediates in the degradation of pollutants in many advanced oxidation processes. However, unlike Mn(III) and Fe(IV), the current exploration of the reaction activity and selective oxidation mechanism of Cu(III) towards pollutants with different structures is still quite limited. Herein, the copper(III) periodate was synthesized to investigate the reactivity towards six sulfonamide antibiotics (SAs) including typical two pentacyclic structures (sulfamethoxazole (SMX) and sulfathiazole (STZ)) and four hexacyclic structures (sulfadiazine (SDZ), sulfamerazine (SMR), sulfamonomethoxine (SMM) and sulfapyridine (SPD)). The results indicated that all SAs almost completely removed by Cu(III) system after 10 min with the molar ratio of approximately 3:1 (Cu(III):SAs) and Cu(III) direct oxidation played the most important role. SAs with 6-ring substituents were more readily degraded by Cu(III) than SAs with 5-ring substituents, and the presence of electron-rich group such as -CH 3 and -S in ring substituent increased the reactivity towards Cu(III). The introduction of coexisting anions (Cl − , SO 4 2− and HCO 3 − ) hardly affected the degradation of SAs by Cu(III) oxidation, while the addition of HA to some extent inhibited SAs degradation. The solution pH greatly affected the degradation of SAs by Cu(III) and the removal efficiencies of SAs roughly followed the rule of neutral > acidic > alkaline. The degradation mechanism of SAs with 5-ring and 6-ring substituents in Cu(III) system mainly included amino nitration, self-coupling, hydroxylation, S-N cleavage in SAs with 5-ring substituents and SO 2 extrusion in SAs with 6-ring substituents. Although the real water matrix inhibited the degradation of SAs to varying degrees, Cu(III) still played a satisfactory performance on SAs degradation especially for electron-rich structure.
研究领域:
环境科学
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化学
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生物学
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产品关联
DOI
PubMed
高影响因子
Journal of Water Process Engineering
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2025
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IF 6.7
Ping Zhang,Xinru Yang,Can Wang,Fuwei Sun,Haibo Liu,Tianhu Chen,Dong Chen,Ziyang Chu,Jin Zhang,Jian Huang,Fazhi Xie
The bimetallic synergistic effect plays a significant role in enhancing the efficiency of antibiotics degradation via hydrogen peroxide (H 2 O 2 ) activation. In this study, the degradation of sulfamethazine sodium (SMT) by H 2 O 2 was comprehensively explored in a system where Cu(II) and Co(II) ions synergistically activate H 2 O 2 in the presence of calcite. The Cu(II)/Co(II)/calcite/H 2 O 2 system using only 1.0 mg/L of Cu(II), exhibits excellent oxidation capacity, enabling complete removal of SMT within 1 h (0.085 min −1 ). This rate is 4.5 and 23.5 times higher than those observed in the Cu(II)/calcite/H 2 O 2 (0.019 min −1 ) and Co(II)/calcite/H 2 O 2 systems (0.0036 min −1 ), respectively. According to scavenger experiments, ESR captures test, and chemical probe experiments, it is determined that Cu(III) primarily contributes to SMT degradation, rather than hydroxyl radicals (·OH), singlet oxygen ( 1 O 2 ), and high valent cobalt-oxo species [e.g. Co(IV)]. The introduction of Co(II) promotes the formation of Cu(III) by accelerating the oxidation of Cu(II). Furthermore, the degradation pathways for SMT are elucidated through UPLC-ESI-MS/MS analysis, and variations in toxicity are rigorously assessed using the ECOSAR program. In summary, this study reveals the highly effective synergistic activation of H 2 O 2 by Cu(II) and Co(II) in the presence of calcite, offering new insights into the comprehensive utilization of calcite in environmental catalysis, particularly for addressing the pollution caused by coexisting heavy metals and antibiotics.
研究领域:
环境科学
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化学工程
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催化
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水污染控制
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高级氧化工艺
✓ 已验证
产品关联
DOI
高影响因子
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