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

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

Abstract

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

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

CLC Number:

X703

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.

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.

Figures/Tables 11

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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]

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]

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