Performance and mechanisms of oxalic acid-modified zero-valent iron catalyzing periodate for sulfamethazine degradation

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

Abstract

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

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

CLC Number:

X703.1

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.

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.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0230

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

Figures/Tables 19

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

Fig.2 Concentration of dissolved iron in different processes

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

Fig.3 Diagram of response surface

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

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

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

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

Fig.8 Density functional theory analysis

Fig.9 DMPO and TEMP spin-trapping EPR spectra

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

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

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

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

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

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

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

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

Fig.18 SMT removal in natural fresh water

References 18

[1]	李威，李佳熙，李吉平，等. 我国不同环境介质中的抗生素污染特征研究进展［J］. 南京林业大学学报（自然科学版），2020，44（1）：205-214．
	LI Wei， LI Jiaxi， LI Jiping，et al. Pollution characteristics of antibiotics in different environment media in China：A review［J］. Journal of Nanjing Forestry University （Natural Sciences Edition），2020，44（1）：205-214．
[2]	刘鹏霄，王旭，冯玲. 自然水环境中抗生素的污染现状、来源及危害研究进展［J］. 环境工程，2020，38（5）：36-42．
	LIU Pengxiao， WANG Xu， FENG Ling. Occurrences，resources and risk of antibiotics in aquatic environment：A review［J］. Environmental Engineering，2020，38（5）：36-42．
[3]	WANG Yifei， YANG Qing， DONG Junqing，et al. Competitive adsorption of PPCP and humic substances by carbon nanotube membranes：Effects of coagulation and PPCP properties［J］. Science of the Total Environment，2018，619：352-359． doi:10.1016/j.scitotenv.2017.11.117
[4]	LING Chen， WU Shuai， HAN Jiangang，et al ．Sulfide-modified zero-valent iron activated periodate for sulfadiazine removal：Performance and dominant routine of reactive species production［J］．Water Research，2022，220：118676． doi:10.1016/j.watres.2022.118676
[5]	DENG Shanshan， LIU Liquan， CAGNETTA G，et al. Mechanochemically synthesized S-ZVIbm composites for the activation of persulfate in the pH-independent degradation of atrazine：Effects of sulfur dose and ball-milling conditions［J］. Chemical Engineering Journal，2021，423：129789． doi:10.1016/j.cej.2021.129789
[6]	朱晓伟，肖广锋，周婷，等. 高碘酸盐的活化及降解水体有机污染物研究进展［J］. 水处理技术，2021，47（3）：7-11． doi:10.16796/j.cnki.1000-3770.2021.03.002
	ZHU Xiaowei， XIAO Guangfeng， ZHOU Ting，et al. Research progress of periodate activation and degradation of organic pollutants in water［J］. Technology of Water Treatment，2021，47（3）：7-11． doi:10.16796/j.cnki.1000-3770.2021.03.002
[7]	BOKARE A D， CHOI W. Singlet-oxygen generation in alkaline periodate solution［J］. Environmental Science & Technology，2015，49（24）：14392-14400． doi:10.1021/acs.est.5b04119
[8]	ZONG Yang， SHAO Yufei， ZENG Yunqiao，et al. Enhanced oxidation of organic contaminants by iron（Ⅱ）-activated periodate：The significance of high-valent iron-oxo species［J］. Environmental Science & Technology，2021，55（11）：7634-7642． doi:10.1021/acs.est.1c00375
[9]	LING Chen， WU Shuai， HAN Jiangang，et al. Sulfide-modified zero-valent iron activated periodate for sulfadiazine removal：Performance and dominant routine of reactive species production［J］．Water Research，2022，220：118676． doi:10.1016/j.watres.2022.118676
[10]	WANG Qun， ZENG Han， LIANG Youheng，et al. Degradation of bisphenol AF in water by periodate activation with FeS （mackinawite） and the role of sulfur species in the generation of sulfate radicals［J］. Chemical Engineering Journal，2021，407：126738． doi:10.1016/j.cej.2020.126738
[11]	LI Huanxuan， WAN Jinquan， MA Yongwen，et al. Influence of particle size of zero-valent iron and dissolved silica on the reactivity of activated persulfate for degradation of acid orange 7［J］. Chemical Engineering Journal，2014，237：487-496． doi:10.1016/j.cej.2013.10.035
[12]	徐晗阳，孙武，李锦祥，等. 预磁化对零价铁反应活性影响的探究［J］. 四川环境，2015，34（6）：15-22．
	XU Hanyang， SUN Wu， LI Jinxiang，et al. Influence of pre- magnetization on reactivity of zero-valent iron［J］. Sichuan Environment，2015，34（6）：15-22．
[13]	XU Jiang， AVELLAN A， LI Hao，et al. Sulfur loading and speciation control the hydrophobicity，electron transfer，reactivity，and selectivity of sulfidized nanoscale zerovalent iron［J］. Advanced Materials，2020，32（17）：1906910． doi:10.1002/adma.201906910
[14]	HU Yue， PENG Xing， AI Zhihui，et al. Liquid nitrogen activation of zero-valent iron and its enhanced Cr（Ⅵ） removal performance［J］. Environmental Science & Technology，2019，53（14）：8333-8341． doi:10.1021/acs.est.9b01999
[15]	张常安，金蕾，黄应平，等. 丙酮冲洗法提高纳米零价铁抗氧化性能［J］. 环境化学，2021，40（3）：790-798．
	ZHANG Chang'an， JIN Lei， HUANG Yingping，et al. Anti-oxidation ability of nanoscale zero valent iron viaacetone flushing method［J］. Environmental Chemistry，2021，40（3）：790-798．
[16]	REN Wei， ZHOU Peng， NIE Gang，et al. Hydroxyl radical dominated elimination of plasticizers by peroxymonosulfate on metal-free boron：Kinetics and mechanisms［J］. Water Research，2020，186：116361． doi:10.1016/j.watres.2020.116361
[17]	AYODELE O B. Structure and reactivity of ZSM-5 supported oxalate ligand functionalized nano-Fe catalyst for low temperature direct methane conversion to methanol［J］. Energy Conversion and Management，2016，126：537-547． doi:10.1016/j.enconman.2016.08.016
[18]	HU Yue， ZHAN Guangming， PENG Xing，et al. Enhanced Cr（Ⅵ） removal of zero-valent iron with high proton conductive FeC₂O₄·H₂O shell［J］. Chemical Engineering Journal，2020，389. doi:10.1016/j.cej.2020.124414

Please choose a citation manager

Content to export