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

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

Abstract

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

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

CLC Number:

X703.1

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.

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.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0101

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

Figures/Tables 15

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

Fig.2 SEM images of α-MnO₂ sample

Fig.3 FTIR spectra of α-MnO₂ samples

Fig.4 XPS spectra of α-MnO₂ sample

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

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

Fig.6 XRD spectra of α-MnO₂ sample

Fig.7 Effect of initial pH on STZ removal

Fig.8 Effect of oxidant concentration on STZ removal

Fig.9 Effect of catalyst dosage on STZ removal

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

Fig.11 Effect of free radical quencher on STZ removal

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

Fig.13 LSV analysis of different systems

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

References 23

[1]	OTTOSEN C F， BJERG P L， KÜMMEL S，et al. Natural attenuation of sulfonamides and metabolites in contaminated groundwater：Review，advantages and challenges of current documentation techniques［J］. Water Research，2024，254：121416. doi:10.1016/j.watres.2024.121416
[2]	XU Qing， ZHU Yangchen， MA Shuai，et al. Substituent structure variances alter degradation pathways of sulfonamides in UV/PAA system：Insights from intermediates，ROS，and DFT calculations［J］. Journal of Hazardous Materials，2025，485：136806. doi:10.1016/j.jhazmat.2024.136806
[3]	QIAO Lukai， HE Liangying， GAO Fangzhou，et al. Deciphering key traits and dissemination of antibiotic resistance genes and degradation genes in pharmaceutical wastewater receiving environments［J］. Water Research，2025，275：123241. doi:10.1016/j.watres.2025.123241
[4]	PASTOR-LOPEZ E J， CASAS M E， HELLMAN D，et al. Nature-based solutions for antibiotics and antimicrobial resistance removal in tertiary wastewater treatment：Microbiological composition and risk assessment［J］. Water Research，2024，261：122038. doi:10.1016/j.watres.2024.122038
[5]	XIAO Junyang， DONG Haoran， LI Yangju，et al. Graphene shell-encapsulated copper-based nanoparticles（G@Cu-NPs） effectively activate peracetic acid for elimination of sulfamethazine in water under neutral condition［J］. Journal of Hazardous Materials，2023，441：129895. doi:10.1016/j.jhazmat.2022.129895
[6]	高璐瑶，刘邦海，代鑫，等. 碱改性污泥生物炭活化过氧乙酸降解磺胺甲唑［J］. 工业水处理，2024，44（11）：132-141.
	GAO Luyao， LIU Banghai， DAI Xin，et al. Degradation of sulfamethoxazole with peroxyacetic acid activated by alkali-modified sludge biochar［J］. Industrial Water Treatment，2024，44（11）：132-141.
[7]	LUO Kaiyuan， SHI Yang， HUANG Rongfu，et al. Activation of periodate by N-doped iron-based porous carbon for degradation of sulfisoxazole：Significance of catalyst-mediated electron transfer mechanism［J］. Journal of Hazardous Materials，2023，457：131790. doi:10.1016/j.jhazmat.2023.131790
[8]	LUO Mengfan， ZHANG Heng， SHI Yang，et al. Electrochemical activation of periodate with graphite electrodes for water decontamination：Excellent applicability and selective oxidation mechanism［J］. Water Research，2023，240：120128. doi:10.1016/j.watres.2023.120128
[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]	SHI Wenxin， ZHANG Chi， ZHAO He，et al. Picolinic acid-mediated Mn（Ⅱ） activated periodate for ultrafast and selective degradation of emerging contaminants：Key role of high-valent Mn-oxo species［J］. Water Research，2024，266：122428. doi:10.1016/j.watres.2024.122428
[11]	YAO Yunjin， ZHANG Lijie， QIU Yongjie，et al. Phase-activity relationship of MnO₂ nanomaterials in periodate oxidation for organic pollutant degradation［J］. Water Research，2024，264：122224. doi:10.1016/j.watres.2024.122224
[12]	SHEN Shitai， ZHOU Xinquan， ZHAO Qindi，et al. Understanding the nonradical activation of peroxymonosulfate by different crystallographic MnO₂：The pivotal role of Mn（Ⅲ） content on the surface［J］. Journal of Hazardous Materials，2022，439：129613. doi:10.1016/j.jhazmat.2022.129613
[13]	YU Yanghai， DONG Hongyu， CHEN Tiansheng，et al. Unraveling the intrinsic mechanism behind the selective oxidation of sulfonamide antibiotics in the Mn（Ⅱ）/periodate process：The overlooked surface-mediated electron transfer process［J］. Water Research，2023，244：120507. doi:10.1016/j.watres.2023.120507
[14]	DU Jiangkun， XIAO Guangfeng， XI Yanxing，et al. Periodate activation with manganese oxides for sulfanilamide degradation［J］. Water Research，2020，169：115278. doi:10.1016/j.watres.2019.115278
[15]	WANG Fengchen， LIU Yang， YIN Jialong，et al. Critical role of oxygen vacancies in catalytic ozonation：Non-radical pathways and enhanced hydroxyl groups［J］. Chemical Engineering Journal，2024，500：156952. doi:10.1016/j.cej.2024.156952
[16]	NDOUN M C， ELLIOTT H A， PREISENDANZ H E，et al. Adsorption of pharmaceuticals from aqueous solutions using biochar derived from cotton gin waste and guayule bagasse［J］. Biochar，2021，3（1）：89-104. doi:10.1007/s42773-020-00070-2
[17]	ZHANG Kaiting， YE Chengsong， LOU Yaoyin，et al. Promoting selective water decontamination via boosting activation of periodate by nanostructured Ru-supported Co₃O₄ catalysts［J］. Journal of Ha-zardous Materials，2023，442：130058. doi:10.1016/j.jhazmat.2022.130058
[18]	FANG Guoge， LI Jialing， ZHANG Chen，et al. Periodate activated by manganese oxide/biochar composites for antibiotic degradation in aqueous system：Combined effects of active manganese species and biochar［J］. Environmental Pollution，2022，300：118939. doi:10.1016/j.envpol.2022.118939
[19]	HE Lei， YANG Chao， DING Jie，et al. Fe，N-doped carbonaceous catalyst activating periodate for micropollutant removal：Significant role of electron transfer［J］. Applied Catalysis B：Environmental，2022，303：120880. doi:10.1016/j.apcatb.2021.120880
[20]	HE Liuyang， YANG Shangding， SHEN Shitai，et al. Novel insights into the mechanism of periodate activation by heterogeneous ultrasonic-enhanced sludge biochar：Relevance for efficient degradation of levofloxacin［J］. Journal of Hazardous Materials，2022，434：128860. doi:10.1016/j.jhazmat.2022.128860
[21]	DENG Jie， CHEN Jiaqing， ZENG Yuxi，et al. Mechanistic insights into ultrafast degradation of electron-rich emerging pollutants by waste cyanobacteria resource utilization［J］. Chemical Engineering Journal，2024，499：155918. doi:10.1016/j.cej.2024.155918
[22]	CHEN Lu， WANG Xiao， SHI Gansheng，et al. The regulation of Lewis acid/basic sites in NaFe bimetal MOXs for the controllable photocatalytic degradation of electron-rich/deficient VOCs［J］. Applied Catalysis B：Environmental，2023，334：122850. doi:10.1016/j.apcatb.2023.122850
[23]	LUO Haoyu， WAN Yi， LI Jie，et al. Mg _x Cu-biochar activated peroxydisulfate triggers reductive species for the reduction and enhanced electron-transfer degradation of electron-deficient aromatic pollutants［J］. Journal of Hazardous Materials，2023，452：131267. doi:10.1016/j.jhazmat.2023.131267

Please choose a citation manager

Content to export

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

α-MnO₂活化高碘酸盐降解水中磺胺噻唑

RichHTML

PDF

Knowledge

Cited

Abstract

Cite this article

share this article

Figures/Tables 15

References 23

Related Articles 12

Recommended Articles

Metrics

Comments

[1]	Zhensong WANG, Xiaoxiao NIU, Tao WU. Exploration of degradation efficiency and mechanism of Amino black 10B in iron-copper internal electrolysis system [J]. Industrial Water Treatment, 2026, 46(2): 62-68.
[2]	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.
[3]	Chuantian WU, Yijie CHEN, Chaomin LIN, Zhangliang LI, Yuezhu YANG, Yuancai LÜ. Biochar loaded nanoscale zero-valent iron activated peroxymonosulfate for the degradation of bisphenol A [J]. Industrial Water Treatment, 2025, 45(11): 165-173.
[4]	Bo WANG, Lijie ZHANG, Junren CHEN, Zian REN, Yuejun QI. Research progress on treatment of antibiotic-containing wastewater by microalgae [J]. Industrial Water Treatment, 2024, 44(8): 44-52.
[5]	Xiaojiao LI, Jianli YANG, Kaihong CAO, Yujie WANG, Jianmin HE. Study on the adsorption performance of sulfathiazole by Coffea Arabica L. husk-derived biochar [J]. Industrial Water Treatment, 2023, 43(4): 130-138.
[6]	Yuwei HUA, Guangyang LIU, Zhongxiao LIU, Jun LÜ, Donghui XU, Yanguo ZHANG. Application progress of MOFs in advanced oxidation process of environmental pollutants [J]. Industrial Water Treatment, 2023, 43(10): 16-25.
[7]	Weijian JIA, Huayu ZHU, Desheng WANG, Baiguo JIANG. Characteristics and mechanism of atrazine removal from water by BDD anode [J]. Industrial Water Treatment, 2022, 42(6): 174-179.
[8]	Qian TIAN, Yong LÜ, Chenguang LI, Yanlei ZHANG, Fengmin LI. Preparation of g-C₃N₄ and its photocatalytic degradation mechanism of Norfloxacin and product toxicity evaluation [J]. Industrial Water Treatment, 2022, 42(11): 84-93.
[9]	Hao Lan,Yuan Wang,Jiayan Huang. Recent advances in photochemical degradation of bisphenol A in water [J]. Industrial Water Treatment, 2020, 40(9): 12-18.
[10]	Yang Fan, Lu Xuemei, Liu Zhiying, Xu Yanhua, Shen Lina, Ji Yekun. Combined process of sodium hypochlorite oxidation and ferric salt precipitation for treating glyphosate in wastewater [J]. INDUSTRIAL WATER TREATMENT, 2017, 37(5): 30-33,34.
[11]	Du Linna, Li Gang, Wang Yang, Pan Xiu, Qiu Boyin. Research progress in the bacterial degradation of azo dyes [J]. INDUSTRIAL WATER TREATMENT, 2015, 35(12): 1-4.
[12]	Zong Yanping, Liu Xianhua, Du Xiwen, Shi Xiaoxuan, Liu Hongxi, Lu Yiren. Experimental study on the catalytic degradation of 2,4,5-trichlorophenol in water withUV/H₂O₂ system [J]. INDUSTRIAL WATER TREATMENT, 2013, 33(5): 47-49,56.

模态框（Modal）标题

Please choose a citation manager

Content to export