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离子液体增强酶催化电解系统的脱氯作用:电子传递、酶活性和二氯甲烷扩散。

Enhanced dechlorination of an enzyme-catalyzed electrolysis system by ionic liquids: Electron transfer, enzyme activity and dichloromethane diffusion.

机构信息

College of Environment, Zhejiang University of Technology, 18 Chao-wang Road, Hangzhou, 310014, China.

Zhejiang Haihe Environmental Technology Co., Ltd., 1389 Danxi Road, Jinhua, 321000, China.

出版信息

Chemosphere. 2021 Oct;281:130913. doi: 10.1016/j.chemosphere.2021.130913. Epub 2021 May 17.

Abstract

Enzyme-catalyzed electrolysis system (EES) is a promising technique for the efficient dechlorination of pollutants. In this study, ionic liquids (ILs) was first introduced to enhance the dichloromethane dechlorination performance of an EES. An imidazole-based IL, 1-ethyl-3-methylimidazole tetrafluoroborate ([EMIM][BF]), was chosen due to its excellent performance on dechlorination enhancement than other three ILs. The cyclic voltammograms with different scan rates shows that the presence of IL increased the apparent electron transfer rate constant (k) from 0.008 to 0.013 s. The calculated surface electroactive species concentration (τ) also increased from 7.8 × 10 to 9.5 × 10 mol cm. Electrochemical impedance spectroscopy analysis illustrates that the IL mainly weakened the interfacial resistance between electrolyte and cathode to accelerate the electron communication in the EES. The introduction of IL facilitated the regeneration of reduced glutathione from oxidized glutathione, whereas inhibited the catalytic activity of dehalogenase via the disruption of secondary structure shown in circular dichroism spectra. The presence of IL was also facilitated the dichloromethane diffusion from electrolyte to cathode. The mass transfer rate constants of dichloromethane (k) increased by 6.9 times after the addition of IL. The optimum volume concentration, pH value, reaction temperature and applied voltage were 20%, 7, 35 °C and -0.8 V vs Ag/AgCl, respectively. The study is helpful to understand the promotion mechanism of IL on the dechlorination performance of EES when it is adopted as a treatment technique.

摘要

酶促电解系统 (EES) 是一种很有前途的技术,可用于高效脱氯污染物。本研究首次将离子液体 (IL) 引入到 EES 中,以提高二氯甲烷的脱氯性能。选择咪唑基 IL 1-乙基-3-甲基咪唑四氟硼酸盐 ([EMIM][BF4]),因为它在脱氯增强方面的性能优于其他三种 IL。不同扫描速率的循环伏安图表明,IL 的存在将表观电子转移速率常数 (k) 从 0.008 增加到 0.013 s。计算得到的表面电活性物质浓度 (τ) 也从 7.8×10 增加到 9.5×10 mol cm。电化学阻抗谱分析表明,IL 主要通过削弱电解质和阴极之间的界面电阻来加速 EES 中的电子传递。IL 的引入促进了还原型谷胱甘肽从氧化型谷胱甘肽的再生,同时通过圆二色光谱显示的二级结构的破坏抑制了脱卤酶的催化活性。IL 的存在还促进了二氯甲烷从电解质向阴极的扩散。加入 IL 后,二氯甲烷的传质速率常数 (k) 增加了 6.9 倍。最佳体积浓度、pH 值、反应温度和施加电压分别为 20%、7、35°C 和-0.8 V vs Ag/AgCl。该研究有助于了解当离子液体作为一种处理技术被采用时,离子液体对 EES 脱氯性能的促进机制。

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