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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Configuration modulation of vermiculite by exfoliation coupled Cu(II) anchoring for boosting removal of tetracycline via synergy of adsorption and photocatalysis

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 · 材料科学 · 化学工程
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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Multiplexed microfluidic chip based flow injection analysis system for simultaneous determination of Fe(III), Mn(II) and Cu(II)

Fang Li,Nuotong Shen,Qingcheng Li,Chen Yang,Limin Zhang,Mingjin Wang

The development of microfluidic flow injection analysis (FIA) system for simultaneous and real-time detection of multiple metal ions is of great importance for environmental monitoring, food safety and industrial field. In this work, a multiplexed microfluidic chip based FIA system was fabricated for simultaneous determination of three metal ions, by using Fe(III), Mn(II) and Cu(II) as models. The multiplexed microfluidic chip based FIA system is composed of three parts, including a multi-channel FIA system for solution manipulation, a group of microfluidic chips for reagents mixing and reaction, and one fiber optic spectrometer for fast and real-time absorbance signal detection. The sample solution and chromogenic reagents were injected into the microfluidic chips to carry out specific colorimetric reactions. Fe(III), Mn(II) and Cu(II) reacts with 5-sulfosalicylic acid, formaldoxime, and bis(cyclohexanone) oxalyldihydrazone, respectively, to generate orange, ember and blue colored solution with peak absorbance at 420 nm, 450 nm, and 600 nm, respectively. The absorbance signal of the generated three channels of solution can be sequentially detected by using only one mini spectrometer. The linear detection range for Fe(III), Mn(II) and Cu(II) is 0.1–20 mg/L, 0.1–12 mg/L and 0.2–12 mg/L, respectively. The limit of detection for Fe(III), Mn(II) and Cu(II) is 0.07, 0.02 and 0.1 mg/L respectively. And the limit of quantification for Fe(III), Mn(II) and Cu(II) is 0.2, 0.07 and 0.3 mg/L, respectively. The recoveries of spiked Fe (III), Mn (II), and Cu (II) in real water samples are between 95.3 % to 106 %. Finally, the developed microfluidic chip based FIA system was successfully applied to simultaneous determination of three metal ions in environmental water samples and zinc smelting solution from zinc hydrometallurgy industry with satisfied results.

CAS / MDL: 370-81-0 5965-83-3
研究领域: 环境科学 · 分析化学
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CHEMICAL ENGINEERING SCIENCE · 2024 · IF 4.1

An eco-friendly wheat straw adsorbent functionalized with mercaptopropionyl for the removal of Cu(II) from aqueous solution

Yong-peng Sun,Gang Wang,Ya-ling Guo,Xiao-yan Zhu

A novel absorbent called mercaptopropionyl wheat straw (MPWS) was prepared through alkali pretreatment and mercaptopropionyl modification for efficient removal of Cu(II) from aqueous solutions. Single factor experiments were conducted to investigate various parameters affecting the adsorption of Cu(II) with MPWS. Adsorption experiments including kinetics, isotherms, thermodynamics, as well as various characterization methods were employed to discuss the mechanism of Cu(II) uptake by MPWS in this study. The results showed that MPWS exhibited high removal capacity for Cu(II), achieving a maximum removal efficiency of 97.28 % under optimal conditions: oscillation rate at 150 rpm, temperature at 303 K, duration at 2 h, pH value at 6.0, and initial concentration of Cu(II) at 100 mg/L. The fitting results indicated that pseudo-second-order kinetic model better described the experimental data while Freundlich model provided a better fit for isothermal data. Thermodynamic calculations confirmed that the adsorptive process was spontaneous and endothermic. Characterization techniques such as FTIR spectroscopy SEM imaging, and EDS analysis confirmed chemisorption between Cu(II) ions and functional groups present on MPWS including sulfhydryl groups, amine groups, hydroxyl groups, and carboxyl groups. Overall, the main mechanisms governing Cu(II) uptake onto MPWS included coordination, ion exchange, electrostatic adsorption, and physical adsorption.

CAS / MDL: 52-90-4
研究领域: 环境科学 · 化学工程 · 材料科学
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International Journal of Electrochemical Science · 2024 · IF 1.3

Development of a highly sensitive electrochemical sensor for dexamethasone detection using Fe3O4/polyaniline-Cu(II) microspheres and hematite nanoparticles

Bin Li,Pingxia Wang

Dexamethasone, a potent synthetic glucocorticoid, is widely used for its anti-inflammatory and immunosuppressive properties. However, its misuse as a performance-enhancing drug in sports has raised concerns among regulatory authorities. To address this issue, an electrochemical sensor based on Fe 3 O 4 /polyaniline (PANI)-Cu(II) microspheres and hematite nanoparticles was developed for the sensitive and selective detection of dexamethasone. The sensor exhibited excellent electrocatalytic activity towards the oxidation of dexamethasone due to the synergistic effect of the high conductivity and large surface area of the Fe 3 O 4 /PANI composite microspheres, the electrocatalytic properties of the loaded copper(II) ions, and the enhanced electron transfer of the hematite nanoparticles. Under optimized conditions, the sensor showed a wide linear range of 0.05–50 μM, with a detection limit of 0.015 μM. The sensor also demonstrated good selectivity, reproducibility (RSD = 3.2 %, n = 5), and long-term stability (92 % retention after 4 weeks). Furthermore, the sensor was successfully applied for the determination of dexamethasone in spiked human serum and urine samples, with recoveries ranging from 97.5 % to 103.5 % and RSDs less than 3.5 %.

研究领域: 分析化学 · 药物分析 · 材料科学
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JOURNAL OF HAZARDOUS MATERIALS · 2021 · IF 10.588

Adsorption properties and recognition mechanisms of a novel surface imprinted polymer for selective removal of Cu(II)-citrate complexes

Yue Sun,Yingpeng Gu,Pengyu Zhang

Cu(II)-citrate (Cu(II)-CA) complex, as one of the components in plating solutions, increases the difficulty of Cu(II) treatment due to its stable structure and high mobility. In this work, a novel surface imprinted polymer (Cu-CA-SIP) for selective removal of Cu(II)-CA complex from aqueous solution is synthesized by using polyethyleneimine (PEI) grafted onto chloromethylated polystyrene (CMP) microspheres. Cu(II)-CA anions are successfully imprinted with the molar ration of 1:1 by Cu-CA-SIP at initial pH 4.0. Nearly 100% removal rate can be achieved even at low Cu(II)-CA concentration (0.5 mmol/L), and the maximum Cu(II) uptake of Cu-CA-SIP reaches 1.38 mmol/g at 303 K. In Cu(II)/Fe(III)-CA, Cu(II)/Ni(II)-CA, Cu(II)/Zn(II)-CA and Cu(II)/Cd(II)-CA systems, the relative selectivity coefficients of Cu-CA-SIP for Cu(II)-CA are 9.66, 2.32, 1.40 and 44.55, respectively. Moreover, Cu-CA-SIP can be retrieved with negligible loss of adsorption capacity after six times of reuse. The Cu-CA-SIP column can effectively treat the actual electroplating wastewater within 114 BV, and can still reach 104 BV after three dynamic cycles. Therefore, an innovative imprinted material is designed for the first time on the basis of coordination-configuration recognition mechanism for the treatment of electroplating wastewater, providing a new insight in developing surface imprinted polymer in environmental remediation.

研究领域: 环境科学 · 材料科学
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NEW JOURNAL OF CHEMISTRY · 2025 ·Vol. 49 ·期 24 ·10338-10356 · IF 2.5

Degradation of reactive black 5 via a Cu(II)/NaIO4-based advanced oxidation process: response surface methodology optimization, kinetic simulation and performance enhancement

Fan Bai,Yanjiao Gao,Yongbo Xiao,Jingyi Yang,Jiaxin Chen,Jing Xiao

In recent years, advanced oxidation based on periodate (PI) has become a research focus for disposal of recalcitrant organics from water due to its efficient oxidizing ability. This study systematically investigated the degradation of reactive black 5 (RB5) by the Cu(II)-activated sodium periodate (NaIO4, SPI) system. The optimal reaction conditions were determined via Box–Behnken response surface methodology as [Cu(II)] = 1.013 ± 0.021 g L−1, [SPI] = 45 ± 2 μM, and pH = 5.7 ± 0.3, achieving a RB5 removal rate of 91.98% (R2 = 0.9901, prediction error <1%). The free radical quenching experiment confirmed that the dominant ROS in the system were ˙OH, 1O2, and IO3˙, and their contribution was IO3˙ > 1O2 > ˙OH. The coexistence anion experiments showed that Cl− (0.1–5.0 mM) and SO42− (0.1–5.0 mM) had almost no effect on the RB5 degradation efficiency, with inhibition rates lower than 1.99% and 3.58%, respectively, while CO32− (1.0 mM) and HCO3− (1.0 mM) led to a decrease of 20.8% and 14.17% in the RB5 degradation rate. In the presence of HA, the degradation efficiency of RB5 was maintained at 89.88–92.66%. The system maintained a removal rate of 73.33–87.66% for RB5 in the simulated actual water bodies (tap water/river water/brewery wastewater). Energy-assisted experiments showed that the activation energy of the reaction was significantly reduced and the kobs values were increased by 10.3 times when the temperature was increased to 40 °C, and the reaction time could be shortened to 2 min (removal rate >98%) after ultraviolet (365 nm, 20 W) coupling. In summary, this study is expected to support the related PI-based advanced oxidation process in stubborn pollutant treatment.

CAS / MDL: 7758-99-8
研究领域: 环境科学 · 水污染处理 · 化学工程
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Environmental Science-Nano · 2021 ·Vol. 8 ·期 9 ·2618-2628 · IF 8.131

Promoted peroxymonosulfate activation by electron transport channel construction for rapid Cu(II)/Cu(I) redox couple circulation

Ting Chen,Zhiliang Zhu,Yujie Bao,Hua Zhang,Yanling Qiu,Daqiang Yin

The effective construction of electron transport channels has essential significance for electron-transfer rate enhancement in REDOX processes during peroxymonosulfate (PMS) activation. This study focuses on the establishment of Cu-involved covalent bonds due to the unique electron configuration of Cu ions. The strategy was achieved by anchoring Cu atoms to an O-doped g-C3N4 (Cu–O–CN) matrix. The C–O–Cu linkage was successfully constructed, derived from the precise incorporation of oxygen. From XAFS, H2-TPR, and solid-ESR characteristic observations, the desired REDOX performance was verified. The constructed C–O–Cu linkages were treated as electron transport channels for electron transfer while reacting with PMS, effectively accelerating the REDOX circulation of the Cu(II)/Cu(I) redox couple and promoting the consecutive generation of active species. Consequently, nearly 100% bisphenol A (BPA) was degraded in the Cu–O–CN/PMS reaction system within 30 min. This demonstrates the effectiveness of Cu–O–CN for PMS activation. The prepared Cu–O–CN exhibited definite stability and potential reusability. This research not only highlights the tailored design of heterogeneous catalysts for PMS activation but also broadens its application in water purification.

研究领域: 环境科学 · 催化化学
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RSC Advances · 2018 ·Vol. 8 ·期 59 ·34151-34160 · IF 2.936

Pyrolytic behavior of a zero-valent iron biochar composite and its Cu(II) removal mechanism

Changjiang Yu,Dashuai Zhang,Xinyu Dong,Qiang Lin

The reduction behavior of Fe3+ during the preparation of a zero-valent iron cocoanut biochar (ZBC8-3) by the carbothermic reduction method was analyzed. Fe3+ was first converted into Fe3O4, which was subsequently decomposed into FeO, and finally reduced to Fe0. A minor amount of γ-Fe2O3 was produced in the process. The isothermal thermodynamic data for the removal of Cu(II) over ZBC8-3 followed a Langmuir model. The Langmuir equation revealed a maximum removal capacity of 169.49 mg g−1 at pH = 5 for ZBC8-3. The removal of Cu(II) over ZBC8-3 fitted well to a pseudo-first-order equation, which suggested that the rate limiting step of the process was diffusion. The Cu(II) removal mechanism on ZBC8-3 involved the reduction of Cu(II) by Fe0 to produce Cu0 and Cu2O, while CC, C–O–, and –O–H formed a complex with Cu(II).

研究领域: 环境科学 · 化学工程 · 材料科学
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POLYMER BULLETIN · 2021 ·Vol. 79 ·期 2 ·1201-1216 · IF 2.87

Characteristics and mechanism of Cu(II) adsorption on prepared calcium alginate/carboxymethyl cellulose@MnFe2O4

Yu Changjiang,Li Han,Ma Haoyue,Zhang Limei,Li Yu,Lin Qiang

A magnetic composite microsphere, calcium alginate (CA)/carboxymethyl cellulose (CMC)@MnFe 2 O 4, was prepared using CA and CMC encapsulated MnFe 2 O 4 through blending and cross-linking for the removal of Cu(II) from aqueous solution. The CA/CMC@MnFe 2 O 4 was characterized in detail by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and X-ray phosphorescence spectroscopy. In addition, various adsorption conditions including the initial pH of Cu(II) solution, equilibrium contact time, and initial Cu(II) concentration were tested. The adsorption data fit better to the Langmuir isotherm and follow the pseudo-second-order model, suggesting that it is a monolayer adsorption process with chemisorption as the rate-limiting step. The maximum adsorption capacity of the CA/CMC@MnFe 2 O 4 was 77.22 mg g −1 at 25 ℃ and pH 5. Cu(II) removal mechanisms of CA/CMC@MnFe 2 O 4 follow ion exchange as well as the formation of complexes as evidenced based on the microstructure analysis and adsorption data fitting.

CAS / MDL: 9004-32-4 10031-43-3
研究领域: 环境科学 · 材料科学 · 化学工程
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POLYMER · 2025 · IF 4.5

Direct synthesis of low-molecular-weight poly(2,6-dimethyl-1,4-phenylene oxide) (LMW-PPO) by Cu(II)-ionic liquids

Ya-Qi Wang,Qing He,Zhi-Yang Zhang,Lei Zhang,Na-Juan Yuan,Yong Liu,Hai-Tao Ren,Xu Han

Although the low molecular weight poly(2,6-dimethyl-1,4-phenyl oxide) (LMW-PPO) has been extensively applied in the field of 5G communication, the complicated procedures involved in the synthesis of LMW-PPO and efficient recovery of the homogeneous catalysts are still challenging nowadays. In this study, five ionic liquids (ILs) have been successfully synthesized, and LWM-PPO is directly synthesized using different Cu(OAc) 2 -ILs complexes as catalysts. Among them, Cu(OAc) 2 - IL(a) not only exhibits the high yield of LWM-PPO (83.68%, M n =3.6✕10 3 ) with the low 3,3’,5,5’-tetramethyl-4,4’-diphenoquinone (DPQ) yield (0.12%) and polydispersity index (PDI, 1.39) in methanol, but also maintains high stability after being recycled for 5 times. In addition, with increasing H 2 O contents in the system from 1.0% to 5.0%, the M n values of PPO decrease from 2.9✕10 3 to 2.4✕10 3 with the narrow PDI values in the range of 1.22-1.45, indicating that trace H 2 O effectively promotes the formation of binuclear Cu(II) complex between Cu(OAc) 2 ·H 2 O and ILs, which then polymerizes 2,6-dimethylphenol (DMP) to LMW-PPO. The synthesized LMW-PPO exhibits high thermostability ( T d5% =427.07-430.52°C), low glass transition temperature ( T g =167.6-180.3°C), and low dielectric constant ( D k =2.14-2.64, 1 GHz) and dielectric loss ( D f =2.83✕10 -3 -4.91✕10 -3 , 1 GHZ), indicating that it is more appropriate to be used in the field of 5G communication. This study provides new insight on the importance of ILs in direct synthesis of LMW-PPO with high performances.

研究领域: 材料科学 · 化学工程 · 高分子化学
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Frontiers in Marine Science · 2021 · IF 4.912

Increased Cu(II) Adsorption Onto UV-Aged Polyethylene, Polypropylene, and Polyethylene Terephthalate Microplastic Particles in Seawater

Han Xiaoxin,Vogt Rolf D.,Zhou Jiaying,Zheng Boyang,Yu Xue,Feng Jianfeng,Lu Xueqiang

Environmental effects of microplastic are rather due to their adsorption capacity of contaminants than themselves. Aging is a key factor influencing adsorption properties of environmental microplastics. In order to clarify this influence, polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET) microplastics with particle sizes of <0.9 mm, 0.9–2 mm, and 2–5 mm were artificially aged in seawater for 12 months. This enabled an assessment of the change in Cu(II) adsorption capacity to the microplastics particles under aging. According to the FTIR spectra, fresh microplastics were oxidized during the UV induced aging process. The adsorption capacities of microplastic were positively correlated with their aging time. After 12-months aging, the amount of Cu(II) adsorbed to the aged microplastics was 1.45–2.92 times higher than on the fresh microplastic particles. For PP and PET, the aging effect increased with decreasing size of the microplastic particles. In the case of PE, particles with the medium particle size (0.9–2 mm) had the strongest aging effect.

研究领域: 环境科学 · 材料科学 · 海洋科学
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DALTON TRANSACTIONS · 2020 ·Vol. 49 ·期 34 ·11851-11858 · IF 4.174

A simultaneously GSH-depleted bimetallic Cu(II) complex for enhanced chemodynamic cancer therapy

Shuhua Cao,Xuezhao Li,Yong Gao,Fahui Li,Kaoxue Li,Xuanxuan Cao,Yiwen Dai,Lirong Mao,Shanshan Wang,Xishi Tai

A bimetallic Cu(II) complex as a novel antitumor chemodynamic therapy agent with glutathione (GSH) depletion properties is successfully synthesized and well characterized. In tumor cells, the Cu2+ ions of the complex are reduced to Cu+ ions by GSH and then catalyzed by the overexpressed H2O2 to generate highly cytotoxic hydroxyl radicals (˙OH) that kill cancer cells. The complex is quickly taken up by cancer cells and distributed in multiple organelles including mitochondria and the nucleus. The complex demonstrates good cytotoxicity toward various cancer cell lines. However, its toxicity toward normal cells is significantly lower than that toward cancer cells due to the limited expression of H2O2. In addition, the complex could arrest the cell cycle of the G0/G1 phase, thereby inducing apoptosis rather than necrosis.

研究领域: 化学 · 药学 · 肿瘤学
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