类普鲁士蓝的制备及其活化PMS降解双酚S

doi:10.16085/j.issn.1000-6613.2023-0803

化工进展 ›› 2023, Vol. 42 ›› Issue (12): 6676-6686.DOI: 10.16085/j.issn.1000-6613.2023-0803

• 资源与环境化工 • 上一篇

类普鲁士蓝的制备及其活化PMS降解双酚S

杨有威¹^,²^,³(), 曾亦婷¹^,², 郭昌胜³, 罗玉霞¹^,², 高艳¹^,², 王春英¹^,²()

^1.矿冶环境污染防控江西省重点实验室，江西赣州 341000
^2.江西理工大学资源与环境工程学院, 江西赣州 341000
^3.中国环境科学研究院环境基准与风险评估国家重点实验室, 北京 100012

收稿日期:2023-05-15 修回日期:2023-07-21 出版日期:2023-12-25 发布日期:2024-01-08
通讯作者: 王春英
作者简介:杨有威（1998—），男，硕士研究生，研究方向为废水处理与资源化技术。E-mail：1287476942@qq.com。
基金资助:
江西省自然科学基金面上项目(20232BAB203040);江西理工大学“青年优秀人才支持计划”(JXUSTQJYX2016003);2020年国家大学生创新创业训练计划(202010407004)

Preparation of Prussian blue and its activation of PMS for degrading bisphenol S

YANG Youwei¹^,²^,³(), ZENG Yiting¹^,², GUO Changsheng³, LUO Yuxia¹^,², GAO Yan¹^,², WANG Chunying¹^,²()

^1.Jiangxi Provincial Key Laboratory of Environmental Pollution Prevention and Control in Mining and Metallurgy, Ganzhou 341000, Jiangxi, China
^2.School of Resources and Environmental Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China
^3.State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China

Received:2023-05-15 Revised:2023-07-21 Online:2023-12-25 Published:2024-01-08
Contact: WANG Chunying

摘要/Abstract

摘要：

通过简单共沉淀法合成了类普鲁士蓝化合物（CoFe-PBA），用于活化过一硫酸盐（PMS）降解有机污染物双酚S（BPS）。使用扫描电镜、X射线衍射、X射线光电子能谱等手段对CoFe-PBA进行表征，结果表明CoFe-PBA由紧密结合的Co₃[Fe(CN)₆]₂构成，为纳米级，表面均匀分布着C、Fe、Co、O元素，具有丰富的活性位点。催化剂投加量300mg/L、PMS投加量400mg/L、pH=5.89条件下，CoFe-PBA/PMS降解体系40min内去除73.77%的BPS，对酸性和共存离子（SO₄^2-、NO₃^-和Cl^-）敏感，碱性环境能促进PMS快速活化，重复实验显示该体系具有良好稳定性，使用4次后仅下降26.70%，活化性能优于其他材料。机理分析表明，CoFe-PBA与PMS相互作用，作用过程中改变了金属位点价态，发生电子转移，产生各种活性物质降解BPS，其主要作用活性物种为¹O₂；产物分析表明，在CoFe-PBA活化PMS系统中，BPS可历经三种路径最终转化为开环产物及CO₂和H₂O。本研究通过低耗能、低成本、快速简易的方法制备CoFe-PBA，可为活化PMS绿色降解BPS提供思路。

关键词: 双酚S, 过硫酸盐活化, 类普鲁士蓝, 过渡金属

Abstract:

A Prussian blue-like compound (CoFe-PBA) was synthesized by a simple co-precipitation method for activating permonosulfate (PMS) to degrade organic pollutant bisphenol S (BPS). CoFe-PBA showed high activity on the removal of bisphenol S from activated PMS. Scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were used to characterize CoFe-PBA. The results showed that CoFe-PBA was composed of Co₃[Fe(CN)₆]₂, which was in nanometer scale. The surface was evenly distributed with C, Fe, Co, O elements, with abundant active sites. Under the conditions of catalyst dosage of 300mg/L, PMS dosage of 400mg/L and pH=5.89, the degradation system of CoFe-PBA/PMS could remove 73.77% BPS within 40min, and it was sensitive to acidic and coexisting ions (SO₄^2-, NO₃^- and Cl^-). The alkaline environment could promote the rapid activation of PMS. Repeated experiments showed that the system had good stability, and its activity only decreases by 26.70% after four repeated uses. The mechanism analysis showed that CoFe-PBA interacts with PMS, which changed the valence state of metal sites and produced various active substances to degrade BPS. The main active species was ¹O₂, and BPS was completely degraded through three degradation processes. The analysis of byproducts indicated BPS could be degraded to ring-opening products and finally be transformed to minerialzed products CO₂ and H₂O. Low energy consumption, low cost, rapid and simple preparation of CoFe-PBA provided ideas for green degradation of bisphenol S by activating PMS.

Key words: bisphenol S, persulfate activation, Prussian blue analogue, transition metal

中图分类号:

X703

杨有威, 曾亦婷, 郭昌胜, 罗玉霞, 高艳, 王春英. 类普鲁士蓝的制备及其活化PMS降解双酚S[J]. 化工进展, 2023, 42(12): 6676-6686.

YANG Youwei, ZENG Yiting, GUO Changsheng, LUO Yuxia, GAO Yan, WANG Chunying. Preparation of Prussian blue and its activation of PMS for degrading bisphenol S[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6676-6686.

图/表 11

图1 CoFe-PBA样品的X射线衍射图

图2 CoFe-PBA的SEM图像[(a)~(e)]、元素分布图[(f)~(j)]和EDS谱图[(k)]

图3 催化剂投加量对BPS去除率的影响及一级动力学拟合（PMS投加量为400mg/L，BPS浓度为20mg/L，反应温度25℃）

图4 PMS投加量对BPS去除率的影响及一级动力学拟合（催化剂投加量为300mg/L，BPS浓度为20mg/L，反应温度25℃）

图5 初始pH对BPS去除率的影响及一级动力学拟合（催化剂投加量为300mg/L，PMS投加量为400mg/L，BPS浓度为20mg/L，反应温度25℃）S2O82-+OH-→•OH+2SO42- (2)

图6 共存离子对BPS去除效果的影响及一级动力学拟合（催化剂投加量为300mg/L，PMS投加量400mg/L，pH=5.89，BPS浓度20mg/L，反应温度25℃，共存离子浓度为10mmol/L）

图7 自由基清除剂对BPS去除效率的影响及一级动力学拟合，基于TEMP和DMPO清除剂的电子顺磁共振谱[(a)反应条件：催化剂投加量为300mg/L，PMS投加量400mg/L，pH=5.89(未调整)，BPS浓度20mg/L，反应温度25℃]

图8 CoFe-PBA/PMS体系反应前后各元素的X射线光电子能谱

图9 总有机碳(TOC)的降解趋势和CoFe-PBA重复使用结果（催化剂投加量为300mg/L，PMS投加量400mg/L，pH=5.89(未调整)，BPS浓度20mg/L，反应温度25℃）

表1 其他类可活化过硫酸盐降解双酚S的实验对比

污染物	浓度 /mg·L^-1	去除时间 /min	去除率 /%	去除速率 /mg·min^-1	参考文献
双酚S	20.0	40	73.77	0.3689	本文
双酚S	20.0	120	84.5	0.1408	[35]
双酚S	5.0	30	97.7	0.1628	[36]
双酚S	5.0	60	92.8	0.0773	[37]
双酚S	2.5	90	100.0	0.0278	[38]
双酚S	10.0	150	97.0	0.0647	[39]

图10 中间产物及BPS降解路径

参考文献 40

1	余翠, 武琳, 陈忠, 等. 双酚S对高脂饮食斑马鱼脂代谢的影响及机制[J]. 南京医科大学学报(自然科学版), 2020, 40(7): 981-985, 1020.
	YU Cui, WU Lin, CHEN Zhong, et al. Effects and mechanism of BPS on lipid metabolism of zebrafish with high-fat diet[J]. Journal of Nanjing Medical University (Natural Sciences), 2020, 40(7): 981-985, 1020.
2	YAMAZAKI Eriko, YAMASHITA Nobuyoshi, TANIYASU Sachi, et al. Bisphenol A and other bisphenol analogues including BPS and BPF in surface water samples from Japan, China, Korea and India[J]. Ecotoxicology and Environmental Safety, 2015, 122: 565-572.
3	JIN Hangbiao, ZHU Lingyan. Occurrence and partitioning of bisphenol analogues in water and sediment from Liaohe River Basin and Taihu Lake, China[J]. Water Research, 2016, 103: 343-351.
4	JI Kyunghee, HONG Seongjin, Younglim KHO, et al. Effects of bisphenol S exposure on endocrine functions and reproduction of zebrafish[J]. Environmental Science & Technology, 2013, 47(15): 8793-8800.
5	HUANG Wei, ZHU Lin, ZHAO Chao, et al. Integration of proteomics and metabolomics reveals promotion of proliferation by exposure of bisphenol S in human breast epithelial MCF-10A cells[J]. The Science of the Total Environment, 2020, 712: 136453.
6	GOYAL Nitin, BARMAN Sanghamitra, BULASARA Vijaya Kumar. Efficient removal of bisphenol S from aqueous solution by synthesized nano-zeolite secony mobil-5[J]. Microporous and Mesoporous Materials, 2018, 259: 184-194.
7	PELAIA Tiana, RUBIN Alexander M, SEEBACHER Frank. Bisphenol S reduces locomotor performance and modifies muscle protein levels but not mitochondrial bioenergetics in adult zebrafish[J]. Aquatic Toxicology, 2023, 257: 106440.
8	IKE M, CHEN M Y, DANZL E, et al. Biodegradation of a variety of bisphenols under aerobic and anaerobic conditions[J]. Water Science and Technology, 2006, 53(6): 153-159.
9	XUE Jingchuan, KANNAN Kurunthachalam. Mass flows and removal of eight bisphenol analogs, bisphenol A diglycidyl ether and its derivatives in two wastewater treatment plants in New York State, USA[J]. Science of the Total Environment, 2019, 648: 442-449.
10	李林, 朱登贵, 孙淑敏, 等. 普鲁士蓝及其类似物作为钠离子电池正极材料的研究进展[J]. 分子科学学报, 2023, 39(1): 1-10.
	LI Lin, ZHU Denggui, SUN Shumin, et al. Research progress of Prussian blue and its analogues as cathode materials for sodium ion batteries[J]. Journal of Molecular Science, 2023, 39(1): 1-10.
11	董沛沛, 冯永强, 王潇, 等. 多孔普鲁士蓝类似物的合成及电催化析氧性能[J]. 精细化工, 2021, 38(4): 823-829.
	DONG Peipei, FENG Yongqiang, WANG Xiao, et al. Synthesis of porous Prussian-blue analogues and electrocatalytic properties for oxygen evolution reaction[J]. Fine Chemicals, 2021, 38(4): 823-829.
12	黎素, 张博, 谢春生, 等. Bi-FeC₂O₄复合催化剂活化过硫酸盐降解罗丹明B[J]. 环境科学学报, 2021, 41(7): 2796-2805.
	LI Su, ZHANG Bo, XIE Chunsheng, et al. Catalytic degradation of Rhodamine B by Bi-FeC₂O₄ composite activated persulfate[J]. Acta Scientiae Circumstantiae, 2021, 41(7): 2796-2805.
13	李英豪, 郑向前, 高晓亚, 等. CoFe₂O₄的制备及其活化过一硫酸盐降解磺胺甲噁唑[J]. 精细化工, 2022, 39(5): 1020-1027.
	LI Yinghao, ZHENG Xiangqian, GAO Xiaoya, et al. Preparation of CoFe₂O₄ and its peroxymonosulfate activation for degradation of sulfamethoxazole[J]. Fine Chemicals, 2022, 39(5): 1020-1027.
14	NIU Lijun, ZHANG Guangming, XIAN Guang, et al. Tetracycline degradation by persulfate activated with magnetic γ-Fe₂O₃/CeO₂ catalyst: Performance, activation mechanism and degradation pathway[J]. Separation and Purification Technology, 2021, 259: 118156.
15	YANG Youwei, GUO Changsheng, ZENG Yiting, et al. Peroxymonosulfate activation by CuFe-Prussian blue analogues for the degradation of bisphenol S: Effect, mechanism, and pathway[J]. Chemosphere, 2023, 331: 138748.
16	LAI Leiduo, YAN Jianfei, LI Jun, et al. Co/Al₂O₃-EPM as peroxymonosulfate activator for sulfamethoxazole removal: Performance, biotoxicity, degradation pathways and mechanism[J]. Chemical Engineering Journal, 2018, 343: 676-688.
17	王磊, 成先雄, 连军锋, 等. 尖晶石型c-CuFe₂O₄催化过硫酸盐降解偶氮染料[J]. 精细化工, 2021, 38(10): 2117-2124.
	WANG Lei, CHENG Xianxiong, LIAN Junfeng, et al. Degradation of azo dye by catalyzed persulfate with spinel c-CuFe₂O₄ [J]. Fine Chemicals, 2021, 38(10): 2117-2124.
18	GHANBARI Farshid, MORADI Mahsa. Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: Review[J]. Chemical Engineering Journal, 2017, 310: 41-62.
19	甄建政,聂士松,潘世元, 等.多维度碳基负载金属催化剂活化PMS降解水中污染物的研究进展[J].化工进展,2022,41(4):1858-1872.
	ZHEN Jianzheng, NIE Shisong, PAN Shiyuan, et al. Research progress on advanced activation of peroxymonosulfate by multidimensional carbon-supported metal catalyst for degradation of organic pollutants in water [J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1858-1872.
20	HUANG Yaohui, HUANG Yi-Fong, HUANG Chuning, et al. Efficient decolorization of azo dye Reactive Black B involving aromatic fragment degradation in buffered Co²⁺/PMS oxidative processes with a ppb level dosage of Co²⁺-catalyst[J]. Journal of Hazardous Materials, 2009, 170(2/3): 1110-1118.
21	董康妮, 谢更新, 晏铭, 等. 磺化生物炭活化过硫酸盐去除水中盐酸四环素[J]. 中国环境科学, 2022, 42(8): 3650-3657.
	DONG Kangni, XIE Gengxin, YAN Ming, et al. Removal of tetracycline hydrochloride from aqueous solutions by sulfonated biochar-activated persulfate[J]. China Environmental Science, 2022, 42(8): 3650-3657.
22	HAMMOUDA Samia Ben, ZHAO Feiping, SAFAEI Zahra, et al. Sulfate radical-mediated degradation and mineralization of bisphenol F in neutral medium by the novel magnetic Sr₂CoFeO₆ double perovskite oxide catalyzed peroxymonosulfate: Influence of co-existing chemicals and UV irradiation[J]. Applied Catalysis B: Environmental, 2018, 233: 99-111.
23	LOU Xiaoyi, WU Liuxi, GUO Yaoguang, et al. Peroxymonosulfate activation by phosphate anion for organics degradation in water[J]. Chemosphere, 2014, 117: 582-585.
24	ZHANG Tao, ZHU Haibo, Jean-Philippe CROUÉ. Production of sulfate radical from peroxymonosulfate induced by a magnetically separable CuFe₂O₄ spinel in water: Efficiency, stability, and mechanism[J]. Environmental Science & Technology, 2013, 47(6): 2784-2791.
25	朱紫琦, 李立, 徐铭骏, 等. 菱形片状铁锰催化剂活化过硫酸盐降解四环素[J]. 中国环境科学, 2021, 41(11): 5142-5152.
	ZHU Ziqi, LI Li, XU Mingjun, et al. Rhombic sheet iron-manganese catalyst-activating peroxymonosulfate for tetracycline degradation[J]. China Environmental Science, 2021, 41(11): 5142-5152.
26	徐铭骏, 郭兆春, 李立, 等. 纳米片状Mn₂O₃@α-Fe₃O₄活化过碳酸盐降解偶氮染料[J]. 化工进展, 2022, 41(2): 1043-1053.
	XU Mingjun, GUO Zhaochun, LI Li, et al. Degradation of azo dyes by sodium percarbonate activated with nanosheet Mn₂O₃@α-Fe₃O₄ [J]. Chemical Industry and Engineering Progress, 2022, 41(2): 1043-1053.
27	LU Hongtao, SUI Minghao, YUAN Bojie, et al. Efficient degradation of nitrobenzene by Cu-Co-Fe-LDH catalyzed peroxymonosulfate to produce hydroxyl radicals[J]. Chemical Engineering Journal, 2019, 357: 140-149.
28	XU Haodan, WANG Da, MA Jun, et al. A superior active and stable spinel sulfide for catalytic peroxymonosulfate oxidation of bisphenol S[J]. Applied Catalysis B: Environmental, 2018, 238: 557-567.
29	HU Enlai, FENG Yafei, NAI Jianwei, et al. Construction of hierarchical Ni-Co-P hollow nanobricks with oriented nanosheets for efficient overall water splitting[J]. Energy & Environmental Science, 2018, 11(4): 872-880.
30	LI Miaoqing, LUO Rui, WANG Chaohai, et al. Iron-tannic modified cotton derived Fe⁰/graphitized carbon with enhanced catalytic activity for bisphenol A degradation[J]. Chemical Engineering Journal, 2019, 372: 774-784.
31	ZHU Shijun, WANG Wei, XU Yongpeng, et al. Iron sludge-derived magnetic Fe⁰/Fe₃C catalyst for oxidation of ciprofloxacin via peroxymonosulfate activation[J]. Chemical Engineering Journal, 2019, 365: 99-110.
32	GUO Ruonan, CHEN Ying, NENGZI Lichao, et al. In situ preparation of carbon-based Cu-Fe oxide nanoparticles from CuFe Prussian blue analogues for the photo-assisted heterogeneous peroxymonosulfate activation process to remove lomefloxacin[J]. Chemical Engineering Journal, 2020, 398: 125556.
33	LU Sen, WANG Guanlong, CHEN Shuo, et al. Heterogeneous activation of peroxymonosulfate by LaCo_1- _x Cu _x O₃ perovskites for degradation of organic pollutants[J]. Journal of Hazardous Materials, 2018, 353: 401-409.
34	胡明珠. 钴铁双金属催化剂活化过硫酸盐降解有机污染物的性能与机理[D]. 杭州: 浙江大学, 2021.
	HU Mingzhu. Performance and mechanism of cobalt-iron bimetallic catalyst activating persulfate to degrade organic pollutants[D]. Hangzhou: Zhejiang University, 2021.
35	WANG Bingyu, LI Qiaoqiao, LV Ying, et al. Insights into the mechanism of peroxydisulfate activated by magnetic spinel CuFe₂O₄/SBC as a heterogeneous catalyst for bisphenol S degradation[J]. Chemical Engineering Journal, 2021, 416: 129162.
36	LIU Yang, GUO Hongguang, ZHANG Yongli, et al. Fe@C carbonized resin for peroxymonosulfate activation and bisphenol S degradation[J]. Environmental Pollution, 2019, 252: 1042-1050.
37	CAI Jing, ZHANG Yan. Enhanced degradation of bisphenol S by persulfate activated with sulfide-modified nanoscale zero-valent iron[J]. Environmental Science and Pollution Research, 2022, 29(6): 8281-8293.
38	WEI Junyan, YIN Linning, QU Ruijuan, et al. Experimental and quantum chemical study on the transformation behavior of bisphenol S by radical-driven persulfate oxidation[J]. Environmental Science: Water Research & Technology, 2022, 8(1): 116-126.
39	SHAO Penghui, DUAN Xiaoguang, XU Jun, et al. Heterogeneous activation of peroxymonosulfate by amorphous boron for degradation of bisphenol S[J]. Journal of Hazardous Materials, 2017, 322: 532-539.
40	HUANG Quanlong, CHEN Congjin, ZHAO Xilian, et al. Malachite green degradation by persulfate activation with CuFe₂O₄@biochar composite: Efficiency, stability and mechanism[J]. Journal of Environmental Chemical Engineering, 2021, 9(4): 105800.

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类普鲁士蓝的制备及其活化PMS降解双酚S

Preparation of Prussian blue and its activation of PMS for degrading bisphenol S

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