<i>α</i>-MnO<sub>2</sub>活化高碘酸盐降解水中磺胺噻唑

doi:10.19965/j.cnki.iwt.2025-0101

摘要/Abstract

摘要：

为高效去除水中磺胺噻唑（STZ），采用水热-煅烧法合成了锰氧化物α-MnO₂，并构建了α-MnO₂/PI（高碘酸盐）高级氧化体系。表征了α-MnO₂的形貌和微观结构，探究了pH、PI浓度、催化剂投加量以及水中常见组分（阴离子和腐殖酸）对α-MnO₂/PI体系降解STZ的影响，并分析了α-MnO₂活化PI的机制。结果表明，在PI浓度为0.25 mmol/L，α-MnO₂投加量为0.15 g/L，初始pH为3.0条件下，体系在6 min内即可完全降解20 μmol/L STZ。HCO₃ ^-对STZ降解表现出显著抑制作用，腐殖酸仅呈现轻微抑制，SO₄ ² ^- 、Cl ^- 、NO₃ ^- 的影响均较小。自由基猝灭实验和电化学分析表明，¹O₂和IO₃·是体系中主要活性氧物种，且α-MnO₂/PI体系在降解STZ时存在电子转移机制。α-MnO₂经4次重复使用后仍保持100%的STZ降解率，表明其具有优异的稳定性和可重复性。α-MnO₂/PI体系展现出对以STZ为代表的多种新污染物的广谱降解能力，显示出良好的实际应用前景。

关键词: 高碘酸盐, α-MnO₂, 磺胺噻唑, 降解机制

Abstract:

Manganese oxide α-MnO₂ was synthesized by hydrothermal-calcination method, and α-MnO₂/PI (periodate) advanced oxidation system was constructed to efficiently remove sulfathiazole (STZ) in water. The morphology and microstructure of α-MnO₂ were characterized. The effects of pH, PI concentration, catalyst dosage and common components (anions and humic acids) in water on the degradation of STZ in α-MnO₂/PI system were investigated, and the mechanism of α-MnO₂ activating PI was analyzed. The results showed that STZ could be completely degraded in 6 min under the conditions of PI concentration of 0.25 mmol/L, α-MnO₂ dosage of 0.15 g/L and initial pH of 3.0. HCO₃ ^- significantly inhibited the degradation of STZ, while humic acid only exhibited slight inhibition. The impacts of SO₄ ^2-, Cl^-, and NO₃ ^- were all minimal. Free radical quenching experiments and electrochemical analysis showed that ¹O₂ and IO₃· were the main reactive oxygen species in the system, and the α-MnO₂/PI system had an electron transfer mechanism during the degradation of STZ. α-MnO₂ still maintained 100% STZ degradation efficiency after 4 times of repeated use, indicating excellent stability and repeatability. α-MnO₂/PI system exhibited a broad-spectrum degradation ability for multiple new pollutants represented by STZ, showing a good practical application prospect.

Key words: periodate, α-MnO₂, sulfathiazole, degradation mechanism

中图分类号:

X703.1

邹智菊, 刘邦海, 任娟, 张露荷, 金春姬. α-MnO₂活化高碘酸盐降解水中磺胺噻唑[J]. 工业水处理, 2026, 46(1): 147-155.

Zhiju ZOU, Banghai LIU, Juan REN, Luhe ZHANG, Chunji JIN. Degradation of sulfathiazole in water by periodate activated with α-MnO₂[J]. Industrial Water Treatment, 2026, 46(1): 147-155.

https://www.iwt.cn/CN/Y2026/V46/I1/147

图/表 15

图1 不同体系中STZ的去除效果（a）和准一级反应动力学速率常数（b）

Fig.1 Removal of STZ in different systems （a） and the quasi-first order reaction kinetics rate constant （b）

图2 α-MnO₂样品的SEM

Fig.2 SEM images of α-MnO₂ sample

图3 α-MnO₂样品的FTIR光谱

Fig.3 FTIR spectra of α-MnO₂ samples

图4 α-MnO₂样品的XPS谱图

Fig.4 XPS spectra of α-MnO₂ sample

图5 α-MnO₂样品的N₂吸附-脱附曲线

Fig.5 N₂ adsorption-desorption curve of α-MnO₂ sample

表1 α-MnO₂样品的比表面积及孔结构参数

Table 1 Specific surface area and pore structure parameters of α-MnO₂ sample

项目	比表面积/（m²·g^-1）	孔体积/（cm³·g^-1）	孔径/nm
数值	36.855	0.098	4.862

图6 α-MnO₂样品的XRD谱图

Fig.6 XRD spectra of α-MnO₂ sample

图7 初始pH对STZ去除效果的影响

Fig.7 Effect of initial pH on STZ removal

图8 氧化剂浓度对STZ去除效果的影响

Fig.8 Effect of oxidant concentration on STZ removal

图9 催化剂投加量对STZ去除效果的影响

Fig.9 Effect of catalyst dosage on STZ removal

图10 阴离子（a~d）和腐殖酸（e）对STZ去除的影响

Fig.10 Effect of anion（a-d） and humic acid（e） on STZ removal

图11 自由基猝灭剂对STZ去除效果的影响

Fig.11 Effect of free radical quencher on STZ removal

图12 α-MnO₂/PI+STZ体系的ESR能谱

Fig.12 ESR spectra of α-MnO₂/PI+STZ system

图13 不同体系线性扫描伏安曲线分析

Fig.13 LSV analysis of different systems

图14 α-MnO₂的循环重复实验（a）和α-MnO₂/PI体系对其他磺胺类污染物的降解性能（b）

Fig.14 Cyclic repetition test of α-MnO₂（a） and degradation of other sulfonamide antibiotic contaminants by the α-MnO₂/PI（b）

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α-MnO₂活化高碘酸盐降解水中磺胺噻唑

Degradation of sulfathiazole in water by periodate activated with α-MnO₂