MnO<sub>2</sub>/Ti电催化膜的制备及其处理乳化油废水性能研究

doi:10.19965/j.cnki.iwt.2023-0389

摘要/Abstract

摘要：

通过简单可控的电沉积方法制备了一种高性能MnO₂包覆Ti基电催化膜（MnO₂/Ti）。系统地表征了所制备的MnO₂/Ti膜形貌、元素含量、价态分布和电化学阻抗以及循环伏安交流测试，并考察了流速和电流密度对MnO₂/Ti膜水处理性能的影响。结果表明，MnO₂均匀分布在Ti膜表面，电沉积MnO₂可以显著提高Ti膜电化学活性，增强Ti膜电催化氧化性能，从而提升Ti膜自清洁能力。在电流密度为10 mA/cm²，流速为1.5 mL/min的工作条件下，乳化油的去除率高达91%。此外，MnO₂/Ti膜具有良好的稳定性和可重复使用性能。氧化机理表明，MnO₂/Ti膜在电催化处理过程中具有直接和间接氧化活性，MnO₂涂层可提高Ti膜的直接氧化能力和·OH、O₂ ^·-产量。

关键词: 多孔钛膜, 膜电极, 电催化膜, 乳化油

Abstract:

A high-performance MnO₂-coated Ti-based electrocatalytic membrane(MnO₂/Ti) was prepared by a simple and controllable electrodeposition method. The morphology, elemental content, valence distribution and electrochemical impedance of the prepared MnO₂/Ti membrane were systematically characterized, as well as cyclic voltammetric AC tests. The effects of flow rate and current density on the water treatment performance of the MnO₂/Ti membrane were investigated. The results showed that MnO₂ was uniformly distributed on the surface of Ti membrane,and electrodeposition MnO₂ can significantly improve the electrochemical activity and enhance the electrocatalytic oxidation performance of Ti membrane, which could improve the self-cleaning ability of Ti membrane. The emulsified oil removal efficiency was as high as 91% under the operating conditions with current density of 10 mA/cm² and flow rate of 1.5 mL/min. In addition,the MnO₂/Ti membrane showed good stability and reusability. The oxidation mechanism showed that the MnO₂/Ti membranes had direct and indirect oxidation activities during the electrocatalytic treatment process, and MnO₂ coating could improve the direct oxidation capacity and ·OH, O₂ ^·- yields of the Ti membrane.

Key words: porous titanium membrane, membrane electrode, electrocatalytic membrane, emulsified oil

中图分类号:

X703.1

刘宝林, 谢陈鑫, 钱光磊, 周立山, 张程蕾, 朱令之. MnO₂/Ti电催化膜的制备及其处理乳化油废水性能研究[J]. 工业水处理, 2024, 44(5): 177-184.

Baolin LIU, Chenxin XIE, Guanglei QIAN, Lishan ZHOU, Chenglei ZHANG, Lingzhi ZHU. Preparation of MnO₂/Ti electrocatalytic membrane and its performance in the treatment of emulsified oil wastewater[J]. Industrial Water Treatment, 2024, 44(5): 177-184.

https://www.iwt.cn/CN/Y2024/V44/I5/177

图/表 12

图1 电催化膜反应器装置

Fig.1 Diagram of electrocatalytic membrane reactor device

图2 基体Ti膜SEM（a）以及MnO₂/Ti膜不同放大倍数的表面SEM：（b）2万倍，（c）5万倍，（d）10万倍

Fig.2 The matrix Ti membrane SEM（a） and the surface SEM of different magnifications of MnO₂/Ti membrane：（b） 20 000×（c） 50 000 ×（d） 100 000×

图3 电催化膜表面EDS总谱图（a）和元素分布图像：（b）O元素；（c）Mn元素

Fig.3 EDS total spectrum（a） and element distribution image of electrocatalytic membrane surface：（b）O element；（c）Mn element

图4 MnO₂/Ti膜的XPS扫描图谱

Fig.4 XPS scan of MnO₂/Ti membrane

图5 CV和EIS测试结果

Fig.5 Results of CV and EIS test

图6 流速对去乳化油除率的影响

Fig.6 Effect of flow rate on demulsified oil removal efficiency

图7 电流密度对乳化油去除率的影响

Fig.7 Effect of current density on demulsified oil removal efficiency

图8 Ti膜与MnO₂/Ti膜的乳化油去除率和膜通量对比

Fig.8 Comparison of emulsified oil removal efficiency and permeate fluxes between Ti and MnO₂/Ti membranes

图9 添加自由基清除剂后油的去除率

Fig.9 Removal efficiency after addition of radical scavenger

图10 MnO₂/Ti膜电极电化学氧化机理

Fig. 10 Electrochemical oxidation mechanism of MnO₂/Ti membrane electrode

图11 循环前表面SEM（a）和循环后表面SEM（b）

Fig.11 SEM of surface before cycling（a） and SEM of surface after cycling（b）

图12 循环6次乳化油去除率与膜通量

Fig.12 Emulsified oil removal efficiency and membrane permeability for 6 cycles

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MnO₂/Ti电催化膜的制备及其处理乳化油废水性能研究

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MnO2/Ti电催化膜的制备及其处理乳化油废水性能研究

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MnO₂/Ti电催化膜的制备及其处理乳化油废水性能研究

Preparation of MnO₂/Ti electrocatalytic membrane and its performance in the treatment of emulsified oil wastewater