铁-氮掺杂碳复合材料活化过硫酸盐降解双酚S

doi:10.19965/j.cnki.iwt.2021-1351

摘要/Abstract

摘要：

非均相铁基材料活化过硫酸盐（PS）是高级氧化工艺中高效活化过硫酸盐的重要手段，如何有效提高铁基催化剂的催化性能一直是研究重点。碳基材料因其丰富而稳定的多孔结构常被用于负载铁活性组分。以一种氨基修饰的铁基金属有机框架化合物NH₂-MIL-101（Fe）为模板，采用一步碳化法制备了铁-氮掺杂碳复合材料（Fe-CNs），通过X射线衍射、扫描电镜和透射电镜等表征手段对Fe-CNs的形貌特征和化学组成进行了分析，并进一步研究了Fe-CNs活化过硫酸盐降解双酚S（BPS）的性能。结果表明，在900 ℃下制备的Fe-CNs-900通过活化PS在70 min内可降解99.3%的BPS，Fe-CNs-900/PS体系具有良好的抵抗共存阴离子和腐殖酸（HA）影响的能力。自由基捕获实验和EPR分析表明，SO₄ ^·-、·OH、O₂ ^·-和¹O₂均存在于Fe-CNs-900/PS体系中，但SO₄ ^·-和¹O₂对BPS的降解起主要作用。

关键词: 过硫酸盐, NH₂-MIL-101（Fe）, 铁-氮掺杂碳复合材料, 双酚S

Abstract:

The activation of persulfate（PS） by heterogeneous iron-based materials is an important means to activate persulfate efficiently in advanced oxidation processes. How to effectively improve the catalytic performance of iron-based catalyst has always been the focus of research. Carbon-based materials are often used to support iron active components because of their rich and stable porous structures. Iron-nitrogen doped carbon composites（Fe-CNs） were prepared by one-step carbonization using an amino-modified iron-based metal organic frame compound NH₂-MIL-101（Fe） as a template，and the morphology and chemical composition of the catalysts were characterized by X-ray diffraction，scanning electron microscopy，transmission electron microscopy and so on. The degradation of bisphenol S（BPS） by Fe-CNs activated persulfate（PS） was further studied. The results showed that the Fe-CNs-900 prepared at 900 ℃ could degrade 99.3% BPS in 70 min by activating PS，and the Fe-CNs-900/PS system had good resistance to the influence of coexisting anions and humic acids. The quenching experiment and EPR analysis showed that，SO₄ ^·-，·OH，O₂ ^·- and ¹O₂ all existed in Fe-CNs-900/PS system，but SO₄ ^·- and ¹O₂ played a major role in the degradation of BPS.

Key words: persulfate, NH₂-MIL-101（Fe）, iron-nitrogen doped carbon composites, bisphenol S

中图分类号:

X703.1
TQ426

刘震, 苏瑞典, 李倩. 铁-氮掺杂碳复合材料活化过硫酸盐降解双酚S[J]. 工业水处理, 2022, 42(11): 127-135.

Zhen LIU, Ruidian SU, Qian LI. Degradation of bisphenol S by activated persulfate by iron-nitrogen doped carbon composites[J]. Industrial Water Treatment, 2022, 42(11): 127-135.

https://gyscl.magtechjournal.com/CN/Y2022/V42/I11/127

图/表 12

图1 Fe-CNs-x的XRD

Fig. 1 XRD patterns of Fe-CNs-x

图2 Fe-CNs-900的SEM和TEM

Fig.2 SEM and TEM images of Fe-CNs-900

图3 Fe-CNs-x的XPS图谱

Fig.3 XPS spectrum of Fe-CNs-x

图4 不同碳化温度下制备的Fe-CNs的催化性能

Fig. 4 Catalytic performance of Fe-CNs prepared at different carbonization temperatures

图5 Fe-CNs-900投加量对BPS降解的影响

Fig. 5 Effects of Fe-CNs-900 dosage on the degradation of BPS

图6 PS投加浓度对BPS降解的影响

Fig. 6 Effects of PS concentration on the degradation of BPS

图7 反应温度对BPS降解的影响

Fig. 7 Effects of reaction temperature on the degradation of BPS

图8 初始pH对BPS降解的影响

Fig. 8 Effects of initial pH on the degradation of BPS

图9 不同共存阴离子对BPS降解的影响

Fig. 9 Effects of various coexisting anions on the degradation of BPS

图10 腐殖酸对BPS降解的影响

Fig. 10 Effects of HA on the degradation of BPS

图11 猝灭剂对BPS降解的影响

Fig. 11 Effects of quencher on the degradation of BPS

图12 Fe-CNs-900/PS体系中自由基的EPR

Fig. 12 EPR spectra of free radical in the Fe-CNs-900/PS system

参考文献 21

1	ROARK M C. Endocrine disruptors and marine systems：Science Direct［J］. Encyclopedia of the World's Biomes，2020：188-194. doi:10.1016/b978-0-12-409548-9.12426-1
2	黄智辉，纪志永，陈希，等. 过硫酸盐高级氧化降解水体中有机污染物研究进展［J］. 化工进展，2019，38（5）：2461-2470.
	HUANG Zhihui， JI Zhiyong， CHEN Xi，et al. Degradation of organic pollutants in water by persulfate advanced oxidation［J］. Chemical Industry and Engineering Progress，2019，38（5）：2461-2470.
3	GAO Jie， HAN Dongqiang， XU Yun，et al. Persulfate activation by sulfide-modified nanoscale iron supported by biochar（S-nZVI/BC） for degradation of ciprofloxacin［J］. Separation and Purification Technology，2020，235：116202. doi:10.1016/j.seppur.2019.116202
4	金晓英，李任超，陈祖亮. 纳米零价铁活化过硫酸钠降解2，4-二氯苯酚［J］. 环境化学，2014，33（5）：812-818. doi:10.7524/j.issn.0254-6108.2014.05.007
	JIN Xiaoying， LI Renchao， CHEN Zuliang. Degradation of 2，4-dichlorophenol by the interaction of nanoscale zero-valent iron with persulfate［J］. Environmental Chemistry，2014，33（5）：812-818. doi:10.7524/j.issn.0254-6108.2014.05.007
5	XUE Xiaofei， HANNA K， ABDELMOULA M，et al. Adsorption and oxidation of PCP on the surface of magnetite：Kinetic experiments and spectroscopic investigations［J］. Applied Catalysis B：Environmental，2009，89（3/4）：432-440. doi:10.1016/j.apcatb.2008.12.024
6	LIU Lu， XU Xing， LI Yanwei，et al. One-step synthesis of “nuclear-shell” structure iron-carbon nanocomposite as a persulfate activator for bisphenol A degradation［J］. Chemical Engineering Journal，2020，382：122780. doi:10.1016/j.cej.2019.122780
7	ZHAN Guowu， ZENG Huachun. Alternative synthetic approaches for metal-organic frameworks：Transformation from solid matters［J］. Chemical Communications，2016，53（1）：72-81. doi:10.1039/c6cc07094a
8	田玉雪，许佩瑶，汪黎东，等. 金属有机框架化合物应用于催化反应研究进展［J］. 应用化工，2018，47（4）：810-812. doi:10.3969/j.issn.1671-3206.2018.04.044
	TIAN Yuxue， XU Peiyao， WANG Lidong，et al. Application of metal organic framework in catalytic reaction［J］. Applied Chemical Industry，2018，47（4）：810-812. doi:10.3969/j.issn.1671-3206.2018.04.044
9	LIN K， HSU F K. Magnetic iron/carbon nanorods derived from a metal organic framework as an efficient heterogeneous catalyst for the chemical oxidation process in water［J］. RSC Advances，2015，5：50790-50800. doi:10.1039/c5ra06043e
10	ZHANG Mengwei， LIN K Y A， HUANG C F，et al. Enhanced degradation of toxic azo dye，amaranth，in water using Oxone catalyzed by MIL-101-NH₂ under visible light irradiation［J］. Separation and Purification Technology，2019，227：115632. doi:10.1016/j.seppur.2019.05.074
11	PU Mengjie， WAN Jinquan， ZHANG Fengzhen，et al. Insight into degradation mechanism of sulfamethoxazole by metal-organic framework derived novel magnetic Fe@C composite activated persulfate［J］. Journal of Hazardous Materials，2021，414：125598. doi:10.1016/j.jhazmat.2021.125598
12	SUN Yong， WANG Yajing， MA Huijun，et al. Fe₃C nanocrystals encapsulated in N-doped carbon nanofibers as high-efficient microwave absorbers with superior oxidation/corrosion resistance［J］. Carbon，2021，178：515-527. doi:10.1016/j.carbon.2021.03.032
13	YANG Limeng， CHEN Wendou， SHENG Cuihong，et al. Fe/N-codoped carbocatalysts loaded on carbon cloth（CC） for activating peroxymonosulfate（PMS） to degrade methyl orange dyes［J］. Applied Surface Science，2021，549：149300. doi:10.1016/j.apsusc.2021.149300
14	YANG Shiying， WANG Ping， YANG Xin，et al. Degradation efficiencies of azo dye Acid Orange 7 by the interaction of heat，UV and anions with common oxidants：Persulfate，peroxymonosulfate and hydrogen peroxide［J］. Journal of Hazardous Materials，2010，179（1/2/3）：552-558. doi:10.1016/j.jhazmat.2010.03.039
15	MA Wenjie， WANG Na， DU Yunchen，et al. One-step synthesis of novel Fe₃C@nitrogen-doped carbon nanotubes/graphene nanosheets for catalytic degradation of Bisphenol A in the presence of peroxymonosulfate［J］. Chemical Engineering Journal，2019，356：1022-1031. doi:10.1016/j.cej.2018.09.093
16	NIE Minghua， DENG Yawen， NIE Shuhua，et al. Simultaneous removal of bisphenol A and phosphate from water by peroxymonosulfate combined with calcium hydroxide［J］. Chemical Engineering Journal，2019，369：35-45. doi:10.1016/j.cej.2019.03.046
17	DU Weiyan， ZHANG Qingzhu， SHANG Yanan，et al. Sulfate saturated biosorbent-derived Co-S@NC nanoarchitecture as an efficient catalyst for peroxymonosulfate activation［J］. Applied Catalysis B：Environmental，2020，262：118302. doi:10.1016/j.apcatb.2019.118302
18	DUAN Pijun， LIU Xinning， LIU Binhua，et al. Effect of phosphate on peroxymonosulfate activation：Accelerating generation of sulfate radical and underlying mechanism［J］. Applied Catalysis B：Environmental，2021，298：120532. doi:10.1016/j.apcatb.2021.120532
19	HUANG Guixiang， WANG Chuya， YANG Chuanwang，et al. Degradation of bisphenol A by peroxymonosulfate catalytically activated with Mn_1.8Fe_1.2O₄ nanospheres：Synergism between Mn and Fe［J］. Environmental Science & Technology，2017，51（21）：12611-12618. doi:10.1021/acs.est.7b03007
20	MA Jie， YANG Yongqi， JIANG X，et al. Impacts of inorganic anions and natural organic matter on thermally activated persulfate oxidation of BTEX in water［J］. Chemosphere，2018，190：296-306. doi:10.1016/j.chemosphere.2017.09.148
21	YANG Lei， BAI Xue， SHI Juan，et al. Quasi-full-visible-light absorption by D35-TiO₂/g-C₃N₄ for synergistic persulfate activation towards efficient photodegradation of micropollutants［J］. Applied Catalysis B：Environmental，2019，256：117759. doi:10.1016/j.apcatb.2019.117759

[1]	张山桥, 杨继涛, 张军, 张珊珊. 硫掺杂生物炭负载铁锰氧化物活化PMS降解四环素及多西环素[J]. 工业水处理, 2026, 46(3): 184-195.
[2]	罗文鹏, 魏平方, 谢水祥, 邓皓. Fe²⁺活化过硫酸盐促进聚磺钻井废液固液分离研究[J]. 工业水处理, 2026, 46(3): 143-150.
[3]	邹磊, 向威, 王怡帆, 周涛, 马凤娟, 刘向荣. 羟胺/磁性铜铁氧体活化过硫酸盐高效降解磺胺甲唑[J]. 工业水处理, 2025, 45(8): 43-52.
[4]	李增强. 非均相光催化活化过硫酸盐处理有机污染物的研究进展[J]. 工业水处理, 2025, 45(7): 19-31.
[5]	张一星, 李芸, 胡慧翔. MnFe₂O₄@水热炭活化过硫酸盐降解四环素的性能与机理研究[J]. 工业水处理, 2025, 45(12): 88-99.
[6]	李海帆, 冯华良, 张召基. 湿式催化过氧化氢氧化处理环氧氯丙烷生产污水研究[J]. 工业水处理, 2025, 45(11): 140-150.
[7]	田雨丝, 吉晋兰, 周明华. 基于改性Fe⁰的非均相电Fenton-过硫酸盐体系降解抗生素[J]. 工业水处理, 2025, 45(11): 53-61.
[8]	郭绍东, 王张羽, 刘赛, 周龙, 尹希. 不同方式活化过硫酸盐对污泥过滤性能及胞外聚合物的影响[J]. 工业水处理, 2025, 45(10): 94-101.
[9]	傅翔宇, 李亚峰, 刘奕含, 崔可清, 王玲萍. 磷酸三丁酯改性生物炭活化PMS降解双酚A的效能[J]. 工业水处理, 2025, 45(1): 87-93.
[10]	张磊, 张进, 闫新龙. 多孔Ni/Co水滑石活化过硫酸盐降解磺胺甲唑研究[J]. 工业水处理, 2024, 44(8): 162-170.
[11]	赵杰, 吴俊峰, 窦艳艳, VIKTOROVICH Fedorov Svyatoslav, 王现丽, 刘彪, 朱新锋, 毛艳丽, 高宏斌. 单原子活化过硫酸盐降解有机污染物研究进展[J]. 工业水处理, 2024, 44(7): 38-46.
[12]	柴瑾, 白雪, 张祉瑶, 胡敏, 石娟, 金鹏康. 顺丁烯二酸活化过硫酸盐降解染料有机物研究[J]. 工业水处理, 2024, 44(6): 151-157.
[13]	张静, 张彦平, 裴佳华, 贾小赛, 李一兵, 吕宁. 铁基污泥炭活化过硫酸盐调理剩余污泥脱水的效能和机理研究[J]. 工业水处理, 2024, 44(3): 142-151.
[14]	黄艳, 邢波, 晏伟, 杨郭, 范凤艳, 张华芳, 汤鲲彪. 钢渣/氮掺杂改性活性炭催化过硫酸盐降解罗丹明B[J]. 工业水处理, 2024, 44(2): 147-156.
[15]	范秀磊, 王申鹏, 张舒, 纪伟, 崔月, 孔熙哲, 吕博文. 铜改性生物炭的制备及催化过硫酸盐去除水体中四环素的研究[J]. 工业水处理, 2024, 44(10): 133-142.

选择文件类型/文献管理软件名称

选择包含的内容