磁铁矿球磨零价铁增效去除水中亚硒酸盐的反应机制

doi:10.11949/0438-1157.20240812

摘要/Abstract

摘要：

为增强零价铁（ZVI）去除水中亚硒酸盐［Se（Ⅳ）］的性能，提出了磁铁矿（Fe₃O₄）球磨掺杂ZVI（BF-ZVI）的改性方法。研究结果表明，溶液初始pH为4.0~8.0，BF-ZVI去除Se（Ⅳ）的反应速率是球磨ZVI（B-ZVI）的1.3~3.1倍；通过建立BF-ZVI体系中铁活性物种与其除Se（Ⅳ）间的相关性分析，明晰了游离态亚铁、结构态亚铁及三价铁在BF-ZVI除 Se（Ⅳ）过程中的关键作用；基于XPS和电化学阻抗表征结果，进一步阐明了球磨作用协同Fe₃O₄能够介导内核铁电子转移，进而实现ZVI对Se（Ⅳ）的增效还原除污。

关键词: 零价铁, 磁铁矿, 铁活性物种, 电子转移, 相关性分析

Abstract:

In order to enhance the performance of zero-valent iron (ZVI) in removing selenite [Se(Ⅳ)] from water, a modification method of magnetite (Fe₃O₄) ball-milled doped ZVI (BF-ZVI) was proposed. The results showed that the reaction rate of Se(Ⅳ) removal by BF-ZVI was 1.3—3.1 times that of the ball-milled ZVI without Fe₃O₄ (B-ZVI) in the range of initial pH 4.0—8.0. The key roles of free ferrous iron, structural ferrous iron and trivalent iron in the process of Se(Ⅳ) removal by BF-ZVI were clarified by the establishment of the correlation analysis between the iron reactive species in the BF-ZVI system and its Se(Ⅳ) removal. Based on the results of XPS and electrochemical impedance characterization, it was further illustrated that ball-milling synergistically with Fe₃O₄ can mediate the electron transfer of inner-core iron, thus enhancing the reduction and decontamination of Se(Ⅳ) by ZVI.

Key words: zero-valent iron, magnetite, iron reactive species, electron transfer, correlation analysis

中图分类号:

X 703.5

钱珺瑶, 王承泽, 张晋华, 刘华, 刘昭睿, 李锦祥. 磁铁矿球磨零价铁增效去除水中亚硒酸盐的反应机制[J]. 化工学报, 2025, 76(1): 385-393.

Junyao QIAN, Chengze WANG, Jinhua ZHANG, Hua LIU, Zhaorui LIU, Jinxiang LI. Reaction mechanism for the enhanced removal of selenite in water by ball-milling of zero-valent iron with Fe₃O₄[J]. CIESC Journal, 2025, 76(1): 385-393.

图/表 6

图1 SEM图及Raman光谱

Fig.1 SEM images and Raman spectrum

图2 不同初始pH下铁基材料的除Se(Ⅳ)反应动力学

Fig.2 Removal kinetics of Se(Ⅳ) by ZVI-based materials at different initial pH

图3 B-ZVI [(a)~(c)] 与BF-ZVI [(d)~(f)] 体系中铁活性物种演化规律

Fig.3 Variations of iron reactive species in system of B-ZVI [(a)—(c)] and BF-ZVI [(d)—(f)]

图4 B-ZVI以及BF-ZVI体系中铁活性物种与Se(Ⅳ)浓度的相关性分析

Fig.4 Correlation analysis of Se(Ⅳ) concentration with iron reactive species in systems of B-ZVI and BF-ZVI

图5 ZVI基材料的极化阻抗曲线(a)及其与Se(Ⅳ)反应后的Se XPS(b)； BF-ZVI增效除Se(Ⅳ)示意图(c)

Fig.5 Polarization impedance spectrums (a) of ZVI-based materials and their Se XPS after reaction with Se(Ⅳ) (b); Schematic diagram for the enhanced removal of Se(Ⅳ) by BF-ZVI (c)

图6 不同因素对BF-ZVI除Se(Ⅳ)动力学的影响规律： (a) BF-ZVI投加量； (b) Se(Ⅳ)初始浓度； (c) 球磨时间； (d) Fe3O4球磨掺杂比； (e) 溶解氧； (f) 连续去除Se(Ⅳ)动力学

Fig.6 Influences of different factors on kinetics of Se(Ⅳ) removal by BF-ZVI: (a) dosages of BF-ZVI; (b) concentrations of Se(Ⅳ); (c) ball-milling time of BF-ZVI; (d) percentage of Fe3O4; (e) dissolved oxygen; (f) consecutive running of BF-ZVI

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