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Microfluidic synthesis of renewable biosorbent with highly comprehensive adsorption performance for copper(II)

Yong Zhu, Zhishan Bai, Bingjie Wang, Linlin Zhai, Wenqiang Luo

《化学科学与工程前沿（英文）》 2017年 第11卷 第2期   页码 238-251 doi: 10.1007/s11705-017-1627-1

摘要： A microsphere biosorbent with uniform size (CV= 1.52%), controllable morphology and component, and high mechanical strength was synthesized from chitosan by microfluidic technology combining with chemical crosslinking and solvent extraction. This chitosan microsphere (CS-MS) was prepared with a two-step solidification process, which was acquired by drying for the enhancement of mechanical property in final. The adsorption behavior of CS-MS towards copper (II) and main influencing factors on adsorption performance were investigated by batch experiments. Kinetic data highlighted dominant chemical bonding along with electrons transferring in adsorption process. Isothermal analysis indicated that adsorption capacity was relevant to the number of active site. All these explorations provided a new direction for preparing highly comprehensive performance sorbent used in heavy metal treatment via microfluidic technology.

关键词： chitosan microsphere     microfluidic technology     adsorption     copper (II)    

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Highly selective detection of copper(II) by a “ligand-free” conjugated copolymer in nucleophilic solvents

Weixing Deng, Pengfei Sun, Quli Fan, Lei Zhang, Tsuyoshi Minami

《化学科学与工程前沿（英文）》 2020年 第14卷 第1期   页码 105-111 doi: 10.1007/s11705-019-1791-6

摘要： The synthesis of -cyclohexyl carbamate-attached fluorene- -phenylene copolymer (PFPNCC) and the use of PFPNCC as a “ligand-free” fluorescent chemosensor for Cu(II) are described. Addition of Cu(II) can efficiently quench the fluorescence of PFPNCC in nucleophilic solvents such as DMF and DMSO, but not in low nucleophilic solvents such as 1,4-dioxane and THF. Ultraviolet-visible spectra of the mixture of the conjugated polymer and Cu(II) indicate the presence of a reduced Cu(I) ion in the solution. Furthermore, fluorescence recovery of PFPNCC observed at low temperature suggests that the quenching and reducing mechanism is most probably due to a photo-induced electron transfer from excited PFPNCC to Cu(II). Our findings provide a novel strategy for highly selective conjugated polymer-based chemosensors for various target analytes, albeit “ligand-free”.

关键词： ligand-free     fluorescent chemosensor     copper     photo-induced electron transfer    

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Insights into influence of aging processes on zero-valent iron modified biochar in copper(II) immobilization

《化学科学与工程前沿（英文）》 2023年 第17卷 第7期   页码 880-892 doi: 10.1007/s11705-022-2282-8

摘要： The zero-valent iron modified biochar materials are widely employed for heavy metals immobilization. However, these materials would be inevitably aged by natural forces after entering into the environment, while there are seldom studies reported the aging effects of zero-valent iron modified biochar. In this work, the hydrogen peroxide and hydrochloric acid solution were applied to simulate aging conditions of zero-valent iron modified biochar. According to the results, the adsorption capacity of copper(II) contaminants on biochar, zero-valent iron modified biochar-1, and zero-valent iron modified biochar-2 after aging was decreased by 15.36%, 22.65% and 23.26%, respectively. The surface interactions were assigned with chemisorption occurred on multi-molecular layers, which were proved by the pseudo-second-order and Langmuir models. After aging, the decreasing of capacity could be mainly attributed to the inhibition of ion-exchange and zero-valent iron oxidation. Moreover, the plant growth and soil leaching experiments also proved the effects of aging treatment, the zero-valent iron modified biochar reduced the inhibition of copper(II) bioavailability and increased the mobility of copper(II) after aging. All these results bridged the gaps between bio-adsorbents customization and their environmental behaviors during practical agro-industrial application.

关键词： zero-valent iron modified biochar     aging processes     copper removal     adsorption     pilot-scale experiments    

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electrolysis cells with biocathodes and driven by microbial fuel cells for simultaneous enhanced Co(II) and Cu(II) removal

Jingya SHEN,Yuliang SUN,Liping HUANG,Jinhui YANG

《环境科学与工程前沿（英文）》 2015年 第9卷 第6期   页码 1084-1095 doi: 10.1007/s11783-015-0805-y

摘要： Cobalt and copper recovery from aqueous Co(II) and Cu(II) is one critical step for cobalt and copper wastewaters treatment. Previous tests have primarily examined Cu(II) and Co(II) removal in microbial electrolysis cells (MECs) with abiotic cathodes and driven by microbial fuel cell (MFCs). However, Cu(II) and Co(II) removal rates were still slow. Here we report MECs with biocathodes and driven by MFCs where enhanced removal rates of 6.0±0.2 mg?L ?h for Cu(II) at an initial concentration of 50 mg?L and 5.3±0.4 mg?L h for Co(II) at an initial 40 mg?L were achieved, 1.7 times and 3.3 times as high as those in MECs with abiotic cathodes and driven by MFCs. Species of Cu(II) was reduced to pure copper on the cathodes of MFCs whereas Co(II) was removed associated with microorganisms on the cathodes of the connected MECs. Higher Cu(II) concentrations and smaller working volumes in the cathode chambers of MFCs further improved removal rates of Cu(II) (115.7 mg?L ?h ) and Co(II) (6.4 mg?L ?h ) with concomitantly achieving hydrogen generation (0.05±0.00 mol?mol COD). Phylogenetic analysis on the biocathodes indicates dominantly accounted for 67.9% of the total reads, followed by (14.0%), (6.1%), (2.5%), (1.4%), and (1.0%). This study provides a beneficial attempt to achieve simultaneous enhanced Cu(II) and Co(II) removal, and efficient Cu(II) and Co(II) wastewaters treatment without any external energy consumption.

关键词： biocathode     microbial electrolysis cell     microbial fuel cell     Cu(II) removal     Co(II) removal    

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A microextraction approach for rapid extraction and separation of Mn(II) and Co(II) using saponified

《化学科学与工程前沿（英文）》 2022年 第16卷 第6期   页码 963-972 doi: 10.1007/s11705-021-2081-7

摘要： In this paper, we proposed a microextraction approach for the extraction and separation of Mn(II) and Co(II) from sulfate solution simulating leachate of spent lithium-ion battery cathode materials using saponified di-(2-ethylhexyl)phosphoric acid system. The effects of the following operational variables were investigated: equilibrium pH, tri-n-butyl phosphate concentration, saponification rate, two-phase ratio and residence time. The results showcased that the microextractor can reach the extraction equilibrium within 20 s, thereby greatly reducing necessary extraction time comparing to that of conventional processes. The volumetric mass transfer coefficient showed 8–21 times larger than that of batch device. With the help of microextractor, 95% of Mn(II) was extracted with a single theoretical stage at a chosen two-phase ratio of 3:1, and the separation factor βMn/Co was as large as 65.5. In the subsequent stripping step, more than 99% of manganese from loaded phase was easily stripped under optimal conditions. The microextraction approach greatly enhances the mass transfer while enabling a continuous and controllable extraction process within a simple structure design. When extracting spent electrode material with microextractors, the comprehensive recovery of mangenese can reach 96%. The microextraction approach has a good applicability in the spent lithium-ion battery cathode materials recycling at both bench and industrial scales.

关键词： extraction equilibrium     mass transfer coefficient     microextraction     multicomponent extraction     di-(2-ethylhexyl)phosphoric acid    

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Copper and zinc interaction on water clearance and tissue metal distribution in the freshwater mussel

Tianxiang XIA, Xuehua LIU

《环境科学与工程前沿（英文）》 2011年 第5卷 第2期   页码 236-242 doi: 10.1007/s11783-010-0218-8

摘要： Copper and zinc interaction on clearance from water and distribution in different tissues was investigated for the freshwater mussel, , under laboratory conditions. Clearance rate of Cu or Zn from water was highly dependent on exposure concentration. Interaction effect was most evident at 300 μg·L Cu exposure and depressed the Zn clearance rate significantly ( <0.05). However, the presence of 100 μg·L and 300 μg·L Zn hardly affected the Cu clearance rate. The 300 μg·L Cu presence enhanced Cu accumulation in each tissue most significantly ( <0.01), but caused Zn content to decrease in the gills by 62% ( <0.05), viscera by 49% ( <0.05) and foot by 31% ( <0.05), and increase in the mantle by 97% ( <0.05) and the muscles by 243% ( <0.05) for different Zn exposure treatments. The response of metal accumulation in various tissues of the test mussels indicated that Zn transferred from the gills, viscera and foot to the mantle and muscles might be one of the important characteristics of the Zn regulatory mechanism by leading to a narrow range of Zn concentration in the different tissues.

关键词： interaction     mussel     copper     zinc     clearance     distribution    

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Identification and assessment of environmental burdens of Chinese copper production from a life cycle

Xiaolong SONG,Jianxin YANG,Bin LU,Bo LI,Guangyuan ZENG

《环境科学与工程前沿（英文）》 2014年 第8卷 第4期   页码 580-588 doi: 10.1007/s11783-013-0599-8

摘要： The environmental burdens of Chinese copper production have been identified and quantified in the context of typical technologies, materials supplies and environmental emissions by a life cycle approach. Primary and secondary copper production using copper ores and scraps, respectively, were analyzed in detail. The flash and bath smelting approaches and the recycling of copper scraps were selected as representative copper production processes. A quantitative analysis was also conducted to assess the influence of material transport distance in copper production. Life cycle assessment (LCA) results showed that resources depletion and human health contribute significantly to environmental burdens in Chinese copper production. In addition, the secondary copper production has dramatically lower environmental burdens than the primary production. There is no obvious distinction in overall environmental burdens in primary copper production by flash or bath smelting approach. However, resources depletion is lower and the damage to human health is higher for flash smelting approach. Ecosystem quality damage is slight for both approaches. Environmental burdens from the mining stage contribute most in all life cycle stages in primary copper production. In secondary copper production, the electrolytic refining stage dominates. Based on the life cycle assessment results, some suggestions for improving environmental performance were proposed to meet the sustainable development of Chinese copper industry.

关键词： copper production     environmental burden     life cycle assessment     refined copper    

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迎接铜工业挑战——低成本处理硫化铜精矿途径的思考

朱祖泽

《中国工程科学》 2000年 第2卷 第2期   页码 87-90

摘要：

对过去10年来铜冶炼的技术进步和铜价格的变化作出的简要回顾指出，未来铜市场的竞争是取决于冶炼技术的生产成本的竞争。坚持自我研究开发和引进相结合才能保证我国铜工业健康稳定发展，并能应付国际竞争。评述了现在强氧化-PS转炉吹炼-火法精炼-电解流程的不足；分析了火湿法联合流程的可能性及依据；新的火湿法联合流程将有更强的竞争优势。

关键词： 未来铜工业     硫化铜精矿     低成本处理    

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Variability of waste copper slag concrete and its effect on the seismic safety of reinforced concrete

《结构与土木工程前沿（英文）》 2022年 第16卷 第1期   页码 117-130 doi: 10.1007/s11709-021-0788-7

摘要： Proven research output on the behavior of structures made of waste copper slag concrete can improve its utilization in the construction industry and thereby help to develop a sustainable built environment. Although numerous studies on waste copper slag concrete can be found in the published literature, no research has focused on the structural application of this type of concrete. In particular, the variability in the strength properties of waste copper slag concrete, which is required for various structural applications, such as limit state design formulation, reliability-based structural analysis, etc., has so far not attracted the attention of researchers. This paper quantifies the uncertainty associated with the compressive-, flexural- and split tensile strength of hardened concrete with different dosages of waste copper slag as fine aggregate. Best-fit probability distribution models are proposed based on statistical analyses of strength data generated from laboratory experiments. In addition, the paper presents a reliability-based seismic risk assessment of a typical waste copper slag incorporated reinforced concrete framed building, considering the proposed distribution model. The results show that waste copper slag can be safely used for seismic resistant structures as it results in an identical probability of failure and dispersion in the drift demand when compared with a conventional concrete building made of natural sand.

关键词： waste copper slag     quantification of variability     goodness-of-fit test     seismic risk assessment     PSDM    

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Microwave enhanced stabilization of copper in artificially contaminated soil

Hua ZHANG, Zhiliang ZHU, Noboru YOSHIKAWA

《环境科学与工程前沿（英文）》 2011年 第5卷 第2期   页码 205-211 doi: 10.1007/s11783-010-0290-2

摘要： Microwave processing was used to stabilize copper ions in soil samples. Its effects on the stabilization efficiency were studied as a function of additive, microwave power, process time, and reaction atmosphere. The stabilization efficiency of the microwave process was evaluated based on the results of the toxicity characteristic leaching procedure (TCLP) test. The results showed that the optimal experimental condition contained a 700 W microwave power, 20 min process time and 3 iron wires as the additive, and that the highest stabilization efficiency level was more than 70%. In addition, the different reaction atmospheres showed no apparent effect on the stabilization efficiency of copper in the artificially contaminated soil. According to the result of the Tessier sequential extraction, the partial species of copper in the contaminated soil was deduced to transform from unstable species to stable states after the microwave process.

关键词： microwave     copper     stabilization    

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Cuprous oxide/copper oxide interpenetrated into ordered mesoporous cellulose-based carbon aerogels for

《化学科学与工程前沿（英文）》 2023年 第17卷 第7期   页码 918-929 doi: 10.1007/s11705-023-2305-0

摘要： The casual discharge of dyes from industrial settings has seriously polluted global water systems. Owing to the abundance of biomass resources, preparing photocatalysts for photocatalytic degradation of dyes is significant; however, it still remains challenging. In this work, a cuprous oxide/copper oxide composite was interpenetrated onto carbon nanosheets of cellulose-based flexible carbon aerogels (Cu2O/CuO@CAx) via a simple freeze-drying-calcination method. The introduction of the carbon aerogel effectively prevents the aggregation of the cuprous oxide/copper oxide composite. In addition, Cu2O/CuO@CA0.2 has a larger specific surface area, stronger charge transfer capacity, and lower recombination rate of photogenerated carriers than copper oxide. Moreover, Cu2O/CuO@CA0.2 exhibited high photocatalytic activity in decomposing methylene blue, with a degradation rate reaching up to 99.09% in 60 min. The active oxidation species in the photocatalytic degradation process were systematically investigated by electron spin resonance characterization and poisoning experiments, among which singlet oxygen played a major role. In conclusion, this work provides an effective method for preparing photocatalysts using biomass resources in combination with different metal oxides. It also promotes the development of photocatalytic degradation of dyes.

关键词： carbon aerogel     photocatalysis     dye degradation     biomass     cuprous oxide/copper oxide    

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Nano-copper ions assembled cellulose-based composite with antibacterial activity for biodegradable personal

《化学科学与工程前沿（英文）》 2023年 第17卷 第10期   页码 1544-1554 doi: 10.1007/s11705-022-2288-2

摘要： The current SARS-CoV-2 pandemic has resulted in the widespread use of personal protective equipment, particularly face masks. However, the use of commercial disposable face masks puts great pressure on the environment. In this study, nano-copper ions assembled cotton fabric used in face masks to impart antibacterial activity has been discussed. To produce the nanocomposite, the cotton fabric was modified by sodium chloroacetate after its mercerization, and assembled with bactericidal nano-copper ions (about 10.61 mg·g–1) through electrostatic adsorption. It demonstrated excellent antibacterial activity against Staphylococcus aureus and Escherichia coli because the gaps between fibers in the cotton fabric allow the nano-copper ions to be fully released. Moreover, the antibacterial efficiency was maintained even after 50 washing cycles. Furthermore, the face mask constructed with this novel nanocomposite upper layer exhibited a high particle filtration efficiency (96.08% ± 0.91%) without compromising the air permeability (28.9 min·L–1). This green, economical, facile, and scalable process of depositing nano-copper ions onto modified cotton fibric has great potential to reduce disease transmission, resource consumption, and environmental impact of waste, while also expanding the range of protective fabrics.

关键词： cellulose-based     nanocomposite     biodegradable antibacterial fabric     nano-copper ions     face masks    

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Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)

《环境科学与工程前沿（英文）》 2022年 第16卷 第8期 doi: 10.1007/s11783-022-1530-y

摘要：

• Simultaneous removal of organic contaminants and Pb(II) was achieved by Mn(VII).

关键词： Permanganate     Pb(II) oxidation     MnO2     pH effect    

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PCDD/Fs emission, risk characterization, and reduction in China’s secondary copper production industry

Haiqian LI, Yonglong LU, Li LI

《环境科学与工程前沿（英文）》 2013年 第7卷 第4期   页码 589-597 doi: 10.1007/s11783-013-0495-2

摘要： Secondary copper production is one of the key polychlorinated dibenzo- -dioxins and dibenzofurans (PCDD/Fs) emission sources in China, but research and data on this issue are rare. In 2004, when the Stockholm Convention entered into force in China, PCDD/Fs emissions from secondary copper production contributed to 32.2% of the total release. In this paper, PCDD/Fs emission dynamics from secondary copper industry were discussed and cumulative risks were characterized. From 2004 to 2009, industrial policies played an indirect role in PCDD/Fs reduction, but its effects are still limited. The Yangtze River Delta, Pearl River Delta and central regions were among the top three of dioxin emissions from secondary copper production in China. Shanghai, Shandong, Zhejiang, and Jiangxi had comparatively higher accumulated risk and were recommended as the priority regions for promoting PCDD/Fs emission control in China. From 2009 to 2015, the PCDD/Fs emission dynamics in the secondary copper industry were presented through simulation. PCDD/Fs emission equations were established, resulting in the recommendation of control technology conversion rate at 30% for small scale smelters and 51%–57% for large and medium-sized enterprises in 2015. In conclusion, both indirect policy and direct control technology retrofitting should be integrated for more effective PCDD/Fs emission reduction in secondary copper industry.

关键词： polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)     secondary copper production     emission     risk     China    

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Field evidence of decreased extractability of copper and nickel added to soils in 6-year field experiments

Bao Jiang, Dechun Su, Xiaoqing Wang, Jifang Liu, Yibing Ma

《环境科学与工程前沿（英文）》 2018年 第12卷 第2期 doi: 10.1007/s11783-017-0990-y

摘要： The phytotoxicity of added copper (Cu) and nickel (Ni) is influenced by soil properties and field aging. However, the differences in the chemical behavior between Cu and Ni are still unclear. Therefore, this study was conducted to investigate the extractability of added Cu and Ni in 6-year field experiments, as well as the link with their phytotoxicity. The results showed that the extractability of added Cu decreased by 6.63% (5.10%–7.90%), 22.5% (20.6%–23.9%), and 6.87% (0%–17.9%) on average for acidic, neutral, and alkaline soil from 1 to 6 years, although the phytotoxicity of added Cu and Ni did not change significantly from 1 to 6 years in the long term field experiment. Because of dissolution of Cu, when the pH decreased below 7.0, the extractability of Cu in alkaline soil by EDTA at pH 4.0 could not reflect the effects of aging. For Ni, the extractability decreased by 18.1% (10.1%–33.0%), 63.0% (59.2%–68.8%), and 22.0% (12.4%–31.8%) from 1 to 6 years in acidic, neutral, and alkaline soils, respectively, indicating the effects of aging on Ni were greater than on Cu. The sum of ten sequential extractions of Cu and Ni showed that added Cu was more extractable than Ni in neutral and alkaline soil, but similar in acidic soil.

关键词： Copper     Nickel     EDTA     Sequential extraction    

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标题 作者 时间 类型 操作

Microfluidic synthesis of renewable biosorbent with highly comprehensive adsorption performance for copper(II)

Yong Zhu, Zhishan Bai, Bingjie Wang, Linlin Zhai, Wenqiang Luo

期刊论文

Highly selective detection of copper(II) by a “ligand-free” conjugated copolymer in nucleophilic solvents

Weixing Deng, Pengfei Sun, Quli Fan, Lei Zhang, Tsuyoshi Minami

期刊论文

Insights into influence of aging processes on zero-valent iron modified biochar in copper(II) immobilization

期刊论文

electrolysis cells with biocathodes and driven by microbial fuel cells for simultaneous enhanced Co(II) and Cu(II) removal

Jingya SHEN,Yuliang SUN,Liping HUANG,Jinhui YANG

期刊论文

A microextraction approach for rapid extraction and separation of Mn(II) and Co(II) using saponified

期刊论文

Copper and zinc interaction on water clearance and tissue metal distribution in the freshwater mussel

Tianxiang XIA, Xuehua LIU

期刊论文

Identification and assessment of environmental burdens of Chinese copper production from a life cycle

Xiaolong SONG,Jianxin YANG,Bin LU,Bo LI,Guangyuan ZENG

期刊论文

迎接铜工业挑战——低成本处理硫化铜精矿途径的思考

朱祖泽

期刊论文

Variability of waste copper slag concrete and its effect on the seismic safety of reinforced concrete

期刊论文

Microwave enhanced stabilization of copper in artificially contaminated soil

Hua ZHANG, Zhiliang ZHU, Noboru YOSHIKAWA

期刊论文

Cuprous oxide/copper oxide interpenetrated into ordered mesoporous cellulose-based carbon aerogels for

期刊论文

Nano-copper ions assembled cellulose-based composite with antibacterial activity for biodegradable personal

期刊论文

Co-present Pb(II) accelerates the oxidation of organic contaminants by permanganate: Role of Pb(III)

期刊论文

PCDD/Fs emission, risk characterization, and reduction in China’s secondary copper production industry

Haiqian LI, Yonglong LU, Li LI

期刊论文

Field evidence of decreased extractability of copper and nickel added to soils in 6-year field experiments

Bao Jiang, Dechun Su, Xiaoqing Wang, Jifang Liu, Yibing Ma

期刊论文