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泡沫钛/ PbO - GN复合电极对环丙沙星的节能电化学降解:电极特性、参数优化及反应机理

Energy-efficient electrochemical degradation of ciprofloxacin by a Ti-foam/PbO-GN composite electrode: Electrode characteristics, parameter optimization, and reaction mechanism.

作者信息

Ma Xiangjuan, He Cong, Yan Yan, Chen Jianming, Feng Huajun, Hu Jinfei, Zhu Hang, Xia Yijing

机构信息

School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou, 310018, China.

School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou, 310018, China.

出版信息

Chemosphere. 2023 Feb;315:137739. doi: 10.1016/j.chemosphere.2023.137739. Epub 2023 Jan 3.

Abstract

Reducing energy comsuption is crucial to commercialize electrochemical oxidation technologies. In this study, a novel PbO composite electrode (Ti-foam/PbO-GN) was successfully fabricated based on a porous titanium (Ti) foam substrate and a β-PbO active layer embedded with multiple graphene (GN) interlayers, and applied as an anode for energy-efficient pulse electrochemical oxidation of ciprofloxacin (CIP). In contrast to PbO and Ti-foam/PbO electrodes, the Ti-foam/PbO-GN electrode surface exhibited a more compact structure, smaller crystal grain size, and greater electrochemical active surface area. CIP removal of 89.7% was obtained with a low energy consumption (EE/O) of 6.17 kWh m under pulse electrolysis conditions with a current density of 25.00 mA cm, pulse frequency of 5000 Hz, and pulse duty cycle of 50.0%. Up to 70.7% of the energy was saved in the pulse current mode compared to the direct current mode. Narrowing the electrode spacing to 2 cm facilitated the mass transfer process and enhanced oxidation efficiency. According to the intermediates identified, the pulse electrolysis of CIP primarily involved hydroxylation of the quinolone ring, breaking of the piperazine ring, defluorination, and decarboxylation processes, and a possible degradation mechanism of CIP was proposed. The continuous oxidation performance of CIP and the relatively low leaching of Pb suggested that the Ti-foam/PbO-GN electrode exhibited excellent stability, repeatability, and safety. The degradation results of CIP in real water also exhibits the great potential of environmental application. As a result, pulse electrochemical oxidation using a Ti-foam/PbO-GN electrode has proven to be an energy-efficient and promising alternative for antibiotic wastewater treatment.

摘要

降低能耗对于电化学氧化技术的商业化至关重要。在本研究中,基于多孔泡沫钛(Ti)基底和嵌入多个石墨烯(GN)中间层的β-PbO活性层,成功制备了一种新型PbO复合电极(泡沫Ti/PbO-GN),并将其用作阳极,用于高效脉冲电化学氧化环丙沙星(CIP)。与PbO电极和泡沫Ti/PbO电极相比,泡沫Ti/PbO-GN电极表面结构更致密,晶粒尺寸更小,电化学活性表面积更大。在电流密度为25.00 mA/cm²、脉冲频率为5000 Hz、脉冲占空比为50.0%的脉冲电解条件下,CIP去除率达到89.7%,能耗低至6.17 kWh/m³。与直流模式相比,脉冲电流模式下可节省高达70.7%的能量。将电极间距缩小至2 cm有利于传质过程并提高氧化效率。根据鉴定出的中间产物,CIP的脉冲电解主要涉及喹诺酮环的羟基化、哌嗪环的断裂、脱氟和脱羧过程,并提出了CIP可能的降解机制。CIP的持续氧化性能和相对较低的Pb浸出表明,泡沫Ti/PbO-GN电极具有优异的稳定性、可重复性和安全性。CIP在实际水中的降解结果也显示出其在环境应用方面的巨大潜力。因此,使用泡沫Ti/PbO-GN电极的脉冲电化学氧化已被证明是一种节能且有前景的抗生素废水处理替代方法。

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