草酸修饰零价铁催化高碘酸盐降解SMT效能和机制研究

doi:10.19965/j.cnki.iwt.2025-0230

摘要/Abstract

摘要：

以磺胺二甲基嘧啶（SMT）为目标污染物，探究了草酸（OA）修饰零价铁（ZVI）催化高碘酸盐（PI）降解SMT的效能和机制。反应30 min后ZVI/PI体系SMT去除率只有1.59%，但OA-ZVI/PI体系反应10 min后SMT去除率可以达到99.37%。扫描电子显微镜、傅里叶红外光谱仪、接触角、X射线光电子能谱仪和密度泛函理论分析证实了OA修饰ZVI可以增强ZVI的反应活性，强化对PI的活化。电子顺磁技术和捕获实验证实OA-ZVI/PI体系中 ·OH、¹O₂、O₂ ^·-、Fe（Ⅳ）和IO₃ ^·-均对SMT降解起作用。OA-ZVI/PI体系对不同抗生素均有去除作用，对实际废水处理也保持较好效果，同时OA-ZVI有着较好的循环使用效果。

关键词: 草酸, 零价铁, 高碘酸盐, 磺胺二甲基嘧啶

Abstract:

Sulfamethazine(SMT) was chosen as the target pollutant to explore the efficiency and mechanism of removing SMT by oxalic-modified zero-valent iron/periodate(OA-ZVI/PI) system. SMT removal efficiency was only 1.59% in ZVI/PI system within 30 min while the SMT removal efficiency could be enhanced to 99.37% in OA-ZVI/PI system within only 10 min. Scanning electron microscopy, Fourier infrared spectrometer, contact angle, X-ray photoelectron spect and density functional theory analysis confirmed that OA modified ZVI could enhance the reactivity of ZVI, and strengthen the activation of PI. EPR technique and capture experiment confirmed ·OH、¹O₂、O₂ ^·-、Fe(Ⅳ) and IO₃ ^·- all played the important role in SMT removal in OA-ZVI/PI system. OA-ZVI/PI system had good performance for removing various pollutants and showed good performance in treating antibiotics in natural freshwater and OA-ZVI also had the good recycle ability.

Key words: oxalic acid, zero-valent iron, periodate, sulfamethazine

中图分类号:

X703.1

陈明杰, 高尚, 李猛, 刘亮, 潘玉伟. 草酸修饰零价铁催化高碘酸盐降解SMT效能和机制研究[J]. 工业水处理, 2025, 45(12): 162-172.

Mingjie CHEN, Shang GAO, Meng LI, Liang LIU, Yuwei PAN. Performance and mechanisms of oxalic acid-modified zero-valent iron catalyzing periodate for sulfamethazine degradation[J]. Industrial Water Treatment, 2025, 45(12): 162-172.

https://www.iwt.cn/CN/Y2025/V45/I12/162

图/表 19

图1 不同工艺对SMT的降解率和不同工艺下降解SMT的k值

Fig.1 SMT removal by different processes and value of k for SMT removal by different processes

图2 不同工艺中溶解铁的质量浓度

Fig.2 Concentration of dissolved iron in different processes

表1 自变量的实验范围和水平

Table 1 Experimental range and levels of the independent variables

因素	水平
因素	-1	0	1
A：OA-ZVI投加量/（g·L^-1）	0.05	0.275	0.50
B：PI投加量/（mmol·L^-1）	0.10	0.55	1.00
C：pH	3	6	9

图3 响应面图

Fig.3 Diagram of response surface

图4 ZVI和OA-ZVI反应前后的SEM（a~c）和EDX（d）

Fig.4 SEM（a-c） and EDX（d） of ZVI and OA-ZVI before and after reaction

图5 ZVI和OA-ZVI反应前后的XPS谱图

Fig.5 XPS spectrum of ZVI and OA-ZVI before and after reaction

图6 ZVI和OA-ZVI反应前后的XRD

Fig.6 XRD of ZVI and OA-ZVI before and after reaction

图7 接触角测试、Tafel和FT-IR分析结果

Fig.7 Results of contact angle measurement， Tafel， and FT-IR analyses

图8 密度泛函理论分析（a）元素；（b）ZVI的晶体结构；（c）PI在ZVI上的吸附能；（d）PI在OA-ZVI上的吸附能。

Fig.8 Density functional theory analysis

图9 DMPO和TEMP捕获自由基的EPR光谱

Fig.9 DMPO and TEMP spin-trapping EPR spectra

图10 使用PMSO探针法检测OA-ZVI/PI体系的结果

Fig.10 Detection results of the OA-ZVI/PI system using the PMSO probe method

图11 添加不同猝灭剂对SMT降解率的影响

Fig.11 Effect of different scavengers on the removal efficiency of SMT

图12 SMT在OA-ZVI/PI中可能的降解路径

Fig.12 The possible pathways for SMT degradation in OA-ZVI/PI process

图13 OA-ZVI/PI体系反应过程中IO₃ ^-和IO₄ ^-的实时浓度

Fig.13 Real-time concentrations of IO₃⁻ and IO₄⁻ during the reaction process in the OA-ZVI/PI system

图14 液相色谱法与淀粉比色法的检测结果

Fig.14 Detection results from high-performance liquid chromatography and the starch colorimetric method

图15 OA-ZVI活化PI的机制

Fig.15 Possible mechanism for activation of PI by OA-ZVI

图16 不同体系对不同污染物的去除效果及去除速率

Fig.16 The comparison of the removal efficiency of different pollutants by different processes

图17 OA-ZVI连续6次循环应用效果

Fig.17 The effect of continuous application of OA-ZVI for 6 cycles

图18 实际水体中不同体系SMT的去除效果

Fig.18 SMT removal in natural fresh water

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