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具有更强配位不饱和金属位点的亚铁金属有机骨架用于过硫酸盐活化,以有效降解废水中的邻苯二甲酸二丁酯。

Ferrous metal-organic frameworks with stronger coordinatively unsaturated metal sites for persulfate activation to effectively degrade dibutyl phthalate in wastewater.

机构信息

College of Environment and Energy, South China University of Technology, Guangzhou, 510006, China; Guangdong Plant Fiber High-Valued Cleaning Utilization Engineering Technology Research Center, Guangzhou, 510006, China.

College of Environment and Energy, South China University of Technology, Guangzhou, 510006, China.

出版信息

J Hazard Mater. 2019 Sep 5;377:163-171. doi: 10.1016/j.jhazmat.2019.05.081. Epub 2019 May 28.

Abstract

In the advanced oxidation system (AOPs) of persulfate (PS) activated by iron-based metal-organic frameworks (MOFs), aim at solving the problem on the treatment difficulty of wastewater with low concentration persistent organic pollutants (POPs), a new type of ferrous metal-organic frameworks (Fe(Ⅱ)-MOFs) with stronger coordinatively unsaturated metal sites (CUS) was successfully synthesized by different methods. The catalytic performance of Fe(Ⅱ)-MOFs was were obtained by the experiment of degrading dibutyl phthalate (DBP) through persulfate activation. It was found that the degradation efficiency of 0.018 mmol L DBP was 86.73% under the conditions of 0.40 g L and 2.70 mmol L persulfate at a wide pH range. At the same time, the crystal structure and surface morphology of Fe(Ⅱ)-MOFs did not change significantly after reaction and it could still maintain the removal rate of 75.44% of the target pollutants in the fifth cycle. Furthermore, in the consideration of iron valence state of MOFs before and after reaction, and combined with the analysis of electrochemical properties, the possible mechanism of PS activation was proposed, namely the metastable electron layer inside ferrous ions produced the internal power to accelerate the electron transfer in CUS, leading to improve the activity of the catalyst.

摘要

在过硫酸盐(PS)激活铁基金属有机框架(MOFs)的高级氧化系统(AOPs)中,针对低浓度持久性有机污染物(POPs)废水处理难度大的问题,采用不同方法成功合成了一种新型具有更强配位不饱和金属位(CUS)的亚铁金属有机框架(Fe(Ⅱ)-MOFs)。通过过硫酸盐活化降解邻苯二甲酸二丁酯(DBP)的实验,得到了 Fe(Ⅱ)-MOFs 的催化性能。结果表明,在 0.40 g/L 和 2.70 mmol/L 过硫酸盐的宽 pH 范围内,0.018 mmol/L DBP 的降解效率为 86.73%。同时,反应后 Fe(Ⅱ)-MOFs 的晶体结构和表面形貌没有明显变化,在第五个循环中仍能保持 75.44%的目标污染物去除率。此外,考虑到 MOFs 反应前后的铁价态,并结合电化学性质分析,提出了 PS 活化的可能机制,即亚铁离子内部的亚稳定电子层产生了加速 CUS 中电子转移的内部动力,从而提高了催化剂的活性。

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