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JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY · 2015 ·Vol. 91 ·期 5 ·1378-1386 · IF 2.349

Hydrazinolyzed cellulose-g-polymethyl acrylate as adsorbent for efficient removal of Cu(II) and Ni(II) ions from aqueous solution

Qiujin Jia,Dongping Li,Xuechuan Gao,Jilong Yan,Qinglin Ma,Fanjun Meng

BACKGROUND Although methyl acrylate has been graft polymerized from cellulose and functionalized with hydrazine and hydroxylamine for removal of copper and nickel ions, the adsorption capacity was less than 80 mg g −1 . The present work reported hydrazinolysis of cellulose-graft-polymethyl acrylate and remarkably improved adsorption capacity for Cu(II) and Ni(II) in aqueous solution. RESULTS Hydrazinolyzed cellulose-graft-polymethyl acrylate (Cell-g-PMA-HZ) has been prepared by ceric salt-initiated graft polymerization of methyl acrylate from microcrystalline cellulose surface and subsequent hydrazinolysis with hydrazine hydrate. The successful synthesis was confirmed by Fourier-transform infrared spectroscopy, 13 C-NMR, elemental analysis, scanning electron microscopy and thermogravimetric analysis. Adsorption behavior of Cell-g-PMA-HZ for Cu(II) and Ni(II) were studied through batch static adsorption processes and column chromatography methods. The influences of graft yield, initial pH, contact time and temperature on adsorption capacity of Cell-g-PMA-HZ as well as adsorption equilibrium, kinetic and thermodynamic properties were studied in detail. Kinetic adsorption can be explained by pseudo-second-order and adsorption isotherms fitted with Langmuir isotherm model, from which maximum equilibrium adsorption capacity can be derived as 229.36 mg g −1 for Cu(II) and 173.91mg g −1 for Ni(II) at 28°C. Further thermodynamic investigation indicated that adsorption of Cu(II) and Ni(II) by adsorbent Cell-g-PMA-HZ was exothermic and spontaneous under the studied conditions. CONCLUSIONS Hydrazinolysis of cellulose-graft-polymethyl acrylate has been accomplished. As an adsorbent, the prepared Cell-g-PMA-HZ was reusable and fairly efficient for removal of Cu(II) and Ni(II) from aqueous solution. © 2015 Society of Chemical Industry

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Science China-Chemistry · 2013 ·Vol. 56 ·期 5 ·567-575 · IF 1.327

Characterization of cellulose-based electrospun nanofiber membrane and its adsorptive behaviours using Cu(II), Cd(II), Pb(II) as models

Xiang Ting,Zhang ZuLei,Liu HaiQing,Yin ZhengZhi,Li Lei,Liu XiaoMing

Nanofiber membranes from the composite of cellulose acetate/polyvinylpyrrolidone were prepared using electrospinning technique. After treated with water and alcoholic KOH to remove partially polyvinylpyrrolidone and deacetylate the cellulose acetate, the membranes were further functionalized with thiol groups using thioglycolic acid. Related materials were characterized using infrared and thermogravimetric analysis. And the results showed that the membranes were success of functionalisation. Then the nanofiber membranes were used in the sorption-desorption process. The effects of pH, contacting time and adsorption capacity of nanofiber membranes were studied against Cu(II), Cd(II) and Pb(II) ions. And the maximum adsorption capacities of Pb (II), Cu (II), and Cd (II) ions were estimated at 30.96, 19.63, 34.70 mg g −1 . Our results suggested that the adsorption behaviour of metal ions could be described using Langmuir model. Their adsorption kinetics was in agreement with the model of pseudo-second order, suggesting chemical adsorption as the rate-limiting step of the adsorption mechanism. The durability of the thiol-functionalized cellulose nanofiber membranes was also evaluated by repetitive adsorption-desorption.

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RSC Advances · 2015 ·Vol. 5 ·期 117 ·96372-96376 · IF 3.84

Cu(II)@Luviset clear as recyclable catalyst for the formation of C–C bond in homo-coupling of terminal alkynes

Zheng-Jun Wang,Peng-Hui Wang,Jing-Jing Lv,Jiu-Ju Feng,Xinhua Xu,Ai-Jun Wang,Chak-Tong Au,Renhua Qiu

Commercial copolymer Luviset clear (L1), an environmentally benign and efficient ligand, was used to facilitate the catalytic performance of Cu(NO3)2 for homo-coupling of terminal alkynes. A series of substituted aromatic and aliphatic terminal alkynes were investigated. It was found that Cu(NO3)2@L1 can catalyze the C–C coupling reactions without any other base, and the corresponding diynes are generated in good to excellent yield. X-ray photoelectron spectroscopy was used to study the reaction mechanism, and the results evidence a Cu(II)/Cu(I) catalytic system. Additionally, the catalyst can be easily separated and reused without showing significant loss of catalytic activity.

CAS / MDL: 536-74-3
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FOOD CHEMISTRY · 2015 · IF 3.391

A sensitive fluorescent sensor for selective determination of dichlorvos based on the recovered fluorescence of carbon dots-Cu(II) system

Juying Hou,Guangjuan Dong,Zhengbin Tian,Jiutian Lu,Qianqian Wang,Shiyun Ai,Minglin Wang

In this paper, a simple and sensitive fluorescent sensor for dichlorvos was first constructed based on carbon dots-Cu(II) system. These carbon dots were obtained by simple hydrothermal reaction of feather. The fluorescence of these carbon dots can be selectively quenched by Cu 2+ ion. When acetylcholinesterase and acetylthiocholine were introduced into the system, thiocholine came into being, which can react with Cu 2+ ion and restore the fluorescence of the system. The reaction mechanism between Cu 2+ ion and thiocholine was confirmed by X-ray photoelectron spectroscopy. As one kind of acetylcholinesterase inhibitor, organophosphorus pesticides can be detected based on this sensing system. As an example of organophosphorus pesticides, dichlorvos was detected with a linear range of 6.0   ×   10 −9 –6.0   ×   10 −8   M. This sensing system has been successfully used for the analysis of cabbage and fruit juice samples.

CAS / MDL: 7558-79-4 7558-80-7
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SENSORS AND ACTUATORS B-CHEMICAL · 2024 · IF 8

Cu(II) coordination MOF-303 based dual-functional sensor for precisely detecting and distinguishing humidity and temperature with multifunction applications

Ke Wu,Lulu Guo,Wei Wang,Zhimin Yang,Haishun Liu

Humidity-temperature dual-functional sensors show great demand in healthcare and archaeology, requiring sensors with high sensitivity, high resolution and high stability. In this work, utilizing the post-coordination strategy, the uncoordinated N atoms in MOF-303 were used as the metal chelate sites to chelate CuCl 2 , and due to the accordion-like morphology, the obtained material shows potential in humidity sensing and temperature sensing. The CuCl 2 -MOF-303 based sensor shows whole range humidity sensing with response of 11.4 at 33 % RH and 56,700 at 95 % RH, 1 % RH of resolution and good long-term stability (>90 days), and excellent temperature sensing performance of high sensitivity (–3.3 %/°C), high linearity (R 2 >0.99) and high resolution (0.3 °C) in the temperature range of 35–38 °C. Furthermore, the application of sensor in healthcare, noncontact sensing and information transmission is verified. This study provides a preliminary exploration for the application of MOFs in humidity-temperature dual-functional sensors.

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Journal of Environmental Chemical Engineering · 2024 · IF 7.4

Facile synthesis of CuOx-decorated TiO2 nanoparticles via oxygen-limited pyrolysis of Cu(II) complex for efficient photocatalytic hydrogen evolution

Chao Yang,Xueying Zhao,Yunlong Zhao,Chenchen Ji,Ronglan Wu,Lu Wang,Xueqing Shao

CuO x -decorated TiO 2 (CuO x /TiO 2 ) nanoparticles have been prepared by the pyrolysis of Cu(II) complex on TiO 2 in an oxygen-limited atmosphere. A solution phase deposition method combined with freeze drying was employed for depositing the 2-methylimidazole-Cu(II) complex onto TiO 2 nanoparticles . The effect of decoration of CuO x on TiO 2 nanoparticles in terms of the crystal phase, morphology, chemical compositions , surface area , surface elemental states, optical absorption and emission properties, was investigated using a series of characterization tools. The oxygen-limited pyrolysis of 2-methylimidazole resulted in the reduction of partial Ti 4+ and Cu 2+ ions into Ti 3+ , Cu + and Cu 0 species, respectively. The surface decoration of CuO x was found to improve the separation and migration of photogenerated electron-hole pairs and increase the life time of excitons. Furthermore, the photocatalytic performance of CuO x /TiO 2 nanoparticles was evaluated for hydrogen evolution in aqueous methanol solution under UV–visible light irradiation . The CuO x /TiO 2 photocatalyst with the optimal cocatalyst loading achieved hydrogen evolution rate of 4.34 mmol h −1 g −1 , with 71- and 5.5-fold enhancement in activity over neat TiO 2 and CuO x /P25, respectively. It is expected that the combination of deposition and pyrolysis of 2-methylimidazole-Cu(II) complex could be an effective approach for the decoration of Cu and its oxides on other supports.

CAS / MDL: 693-98-1 13825-74-6
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Peroxymonosulfate activation by vacuum ultraviolet and trace copper ions: A new way to boost Cu(II)/Cu(I) redox cycle

Bin Zhang,Ziwen Han,Yanjun Xin,Yanjie Zhang,Wenqian Li,Boda Li,An Ding,Jun Ma,Xu He

Herein, vacuum ultraviolet (VUV) was introduced to enhance the activation rate of peroxymonosulfate (PMS) by copper ions for the first time. Compared with ultraviolet (UV), the redox cycle rate of Cu(II)/Cu(I) was prominently enhanced by VUV due to the combined driving effect of UV, hydrated electron and active hydrogen atoms. The accelerated Cu(II)/Cu(I) cycle in VUV/PMS/Cu(II) system led to 2.89 times higher degradation efficiency of 2,4-dichlorophenol (2,4-DCP) than that by UV/PMS/Cu(II) system. More importantly, the initial Cu(II) concentration (5 μM) in VUV/PMS/Cu(II) system was only 1/5 of the guideline value in WHO standards for drinking water, and the initial PMS concentration was also 1 order of magnitude lower than that in most PMS based systems for water treatment. Furthermore, the reaction mechanism and possible degradation pathways of 2,4-DCP were also proposed. This study verified the possibility for the utilization of trace Cu(II) in water to decompose refractory micro-pollutants by PMS activation.

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JOURNAL OF MOLECULAR LIQUIDS · 2024 · IF 5.3

Study on Cu(II) extraction process optimization and mechanism from acidic leaching solution using the deep eutectic solvent P507/Menthol

Jue Chen,Hexiang Zhong,Shan Zhu

In this study, the selectivity of a hydrophobic deep eutectic solvent (HDES) comprising 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (P507) and L-menthol (Men) was assessed for the extraction and separation of Cu(II), Co(II), and Ni(II) from acidic leaching solutions, aiming to make the HDES system more consummate and provide a novel approach for metal extraction using HDES. The results indicated that under the conditions of a 2:1 M ratio of P507 to Men, an extraction temperature of 40℃, an extraction time of 40 min, an oil-water ratio(O/W, v/v) of 1, and a pH value of 4, the three-stage cross-flow extraction efficiency of the HDES for Cu(II) was over 99 %. Furthermore, successful selective separation of Cu(II), Ni(II), and Co(II) was demonstrated by separation coefficients β Cu/Ni of 2150 and β Cu/Co of 305. Molecular dynamics (MD) simulations and density functional theory (DFT) indicated that the formation of an HDES molecule involved the combination of two molecules of P507 and one molecule of Men through hydrogen bonding interactions. Moreover, compared to other cupric complex configurations, the tetrahedral cupric complex, synthesized using two molecules of P507 and two molecules of menthol with Cu(II), exhibited a lower single-point energy and a higher ΔE(LUMO-HOMO), demonstrating greater stability.

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JOURNAL OF FLUORESCENCE · 2025 · IF 3.1

Determination of Trace Cu(II) Ions Using a Siraitia Grosvenorii Residue-derived Nitrogen-doped Carbon Dots-enabled Fluorescence Quenching Sensor

Wu Mengying,Huang Xiyang,Li Zhouquan,Gan Xiang,Zheng Yumei,Tang Hui,Xiong Jingwei,Yang Xiaoli,Yang Dongye,Zhang Lizhen,Liang Weiyuan,Li Hongtao

Bio-based fluorescent carbon dots (CDs) have emerged as promising material for advanced sensing applications due to their exceptional sensitivity, stability and biocompatibility. However, it was till constrained by ion selectivity and solution suitability especially in physiological solutions (e.g., PBS). Herein, a novel nitrogen-doped carbon dots (N-CDs) fluorescence quenching sensor derived from Siraitia grosvenorii (named “Luo Han Guo” in China) residue was developed for selective determination of trace Cu(II) ions in different solutions. The N-CDs were synthesized through a one-step hydrothermal process utilizing agricultural waste as carbon precursor and urea as the nitrogen source, demonstrating an eco-friendly synthesis strategy. The developed sensor exhibited remarkable anti-interference capability against acid, base, salt and various metal ions while maintaining excellent photostability and biocompatibility (cell viability > 75% at 1000 ug/mL). With a limit of detection (LOD) of 0.13 µmol/L, the system showed superior sensitivity compared to conventional methods. Furthermore, the sensor demonstrated strong universality across solution types and, more importantly, suitability for trace Cu²⁺ quantification in physiological solutions. Experimental results demonstrated that the fluorescence quenching process resulted from the binding of Cu²⁺ to amino groups on CDs, forming complexes through a non-radiative photoinduced electron transfer (PET) mechanism. This PET effect synergizes with static quenching, underlying the high selectivity and sensitivity of N-CDs for Cu²⁺ detection. The integration of novel phytochemical-based sensing materials with a fluorescence quenching mechanism enables highly selective detection of trace Cu²⁺ for environmental and biomedical applications.

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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Ratiometric electrochemical biosensor based on Cu(II) modified covalent organic framework for the ultra-sensitive and specific detection of glutathione

Zeyun Yang,Hao Guo,Zhiguo Yu,Mingyue Wang,Xiaoqin Wei,Zongyan Lu,Lei Sun,Henglong Ren,Wu Yang

As a vital biological polypeptide molecule, glutathione (GSH) is involved in the regulation of various life activities. Accurate and sensitive detection of GSH in human body is of great significance for the preliminary diagnosis of related diseases. In this research, Cu(II) modified TADH COF, which has been prepared by Cu 2+ post-synthesis modification of the COF obtained through a condensation reaction of 1,3,5-(4-aminophenyl) benzene (TAPB) and 2,5-dihydroxy-1,4-benzenedicarboxaldehyde (DHTP), and methylene blue (MB) molecules are combined to construct a ratiometric electrochemical sensor for achieving specific and ultra-sensitive detection of GSH. As a stable and active covalent organic framework material, TADH COF possesses the special O(–OH) and N(C N) binding sites, which can load and coordinate with Cu 2+ effectively. The obtained Cu(II)-TADH COF serves as a sensitive electrode material for sensing GSH due to “extrusion effect” caused CuCl solid-state electrochemical signal degeneration by the specific binding of Cu and GSH while MB provides a stable electrical signal in the electrochemical sensing process as an internal reference for eliminating errors and making the detection results more accurate. The constructed electrochemical sensing platform Cu(II)-TADH COF/MB/GCE exhibited an ultrahigh sensitivity with a limit of detection (LOD) of 0.0093 nM (S/N = 3), wide linear range of 0.05 nM–40 μM and high accuracy. For the detection of GSH in real samples including human blood, serum and urine samples, the sensor also showed excellent sensing performance. This is the first research on ratiometric electrochemical sensing platform for the ultra-sensitive detection of glutathione based on covalent organic frameworks, which provides an original and novel strategy for the electrochemical detection of GSH with COF materials.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Revealing the contribution of Cu(II) and Cu(I) inherent in MOF-199 for efficient thiophene removal at room temperature

Mingxian Duan,Yeshuang Wang,Huiling Fan,Zhelin Su,Chao Yang,Jiawei Kou,Ju Shangguan

Thiophene (C 4 H 4 S) removal from coke oven gas is critical to its subsequent high valuable utilization but remains a challenge. MOF-199 was considered as a promising candidate for C 4 H 4 S adsorption removal owing to its nature of enriched opened Cu sites. However, the presence of mixed valence of Cu(II) and Cu(I) in MOF-199 makes it puzzling to their respective contribution to the removal of C 4 H 4 S. Herein, a series of MOF-199 with different Cu(I) contents were synthesized using different methods, including hydrothermal, solution diffusion, and ultrasonic, and their C 4 H 4 S adsorption performance were investigated. The respective contributions of Cu(II) and Cu(I) to the C 4 H 4 S removal was systematically discussed. The collected results indicated that although the samples prepared with different methods present a remarkable difference in textural characters, the latter was found to have a negligible influence on the C 4 H 4 S removal owing to MOF-199(H) affording an inferior surface area and pore volumes but performing the best C 4 H 4 S removal capacity of 53.7 mg S/g. The co-adsorption results of CH 3 SCH 3 and C 4 H 4 S indicated that the excellent performance of MOF-199(H) mainly attributed to the presence of Cu(I), which provides active sites for C 4 H 4 S adsorption through π complex coordination. Cu(II) species was also found to the C 4 H 4 S adsorption via soft-acid-base coordinated interaction, but its contribution is 8.3 mg S/g, only accounting for 15.5 %. Additionally, the adsorption of C 4 H 4 S on MOF-199(H) was found to follow the intra-particle diffusion model and the Langmuir models. Moreover, MOF-199(H) also exhibited an excellent regeneration performance due to the weak interaction between C 4 H 4 S and their opened Cu sites, the C 4 H 4 S adsorption capacity still reaches 50.6 mg S/g after three regeneration cycles, about 94 % of its initial value. The results collected in this study will provide new insights for the manipulation of performance of C 4 H 4 S adsorption on the MOF-199.

CAS / MDL: 554-95-0
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY · 2022 ·Vol. 169 ·期 3 ·037529 · IF 4.386

Blocking the Cu (II) Ions Mediated Catalytical Ability for Construction of Ratiometric Fluorescence Sensing Platform Based on Glutathione-Stabilized Copper Nanoclusters

Bei-Bei Tao,Ning-Ning Wu,Hong-Ding Zhang,Hai-Bo Wang

It is of great importance to integrate two kinds of fluorescent probes in one system to construct ratiometric sensing platform. Inspired by the efficient overlapped spectrum of glutathione-stabilized copper nanoclusters (GSH-CuNCs) and 2, 3-diaminophenazine (DAP), a novel and label-free ratiometric fluorescent sensor has been developed for Cu2+ and kojic acid (KA) detection on the basis of in situ converting o-phenylenediamine (OPD) into DAP by the catalytic oxidation ability of Cu2+. The Cu2+ catalytically generated DAP was served as an energy acceptor to inhibit the fluorescence emission of GSH-CuNCs (energy donor). As a result, the sensitivity and accuracy of the strategy were greatly improved due to the dual-emission reverse change ratiometric profile. The sensing system showed high sensitivity toward Cu2+ in a range of 0.1–50 μM and with a limit of detection of 20 nM. Furthermore, based on the specific coordination interaction between Cu2+ and KA, the ratiometric sensor displayed the range of detection of KA from 0.2 μM to 300 μM with a limit of detection of 50 nM. Thus, the ratiometric method paved a new way for the effective quantification of Cu2+ and KA in real samples, which were closely concerned with human health.

研究领域: 分析化学 · 生物医学
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