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

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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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