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氨基酸功能化金属有机骨架的明显优势:作为过硫酸盐激活剂用于双酚 F 的降解。

The obvious advantage of amino-functionalized metal-organic frameworks: As a persulfate activator for bisphenol F degradation.

机构信息

Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, Qingdao 266200, PR China.

Department of Administrative Examination and Approval Service, Qingdao High-tech Zone, Qingdao 266109, PR China.

出版信息

Sci Total Environ. 2020 Nov 1;741:140464. doi: 10.1016/j.scitotenv.2020.140464. Epub 2020 Jun 25.

Abstract

In this study, two iron-based metal-organic framework compounds (MOFs), were used and compared as catalysts for persulfate (PS) activation to degrade bisphenol F (BPF). The outstanding advantage of using amino-functionalized MOFs in the catalytic system was verified under different reaction conditions, and the mechanism was explored. The results indicated that NH-MIL-101(Fe)/PS system not only had a wide pH application range, but also possessed an excellent catalytic performance towards interference from the coexisting anions and humic acid. Density functional theory (DFT) calculations showed that, compared with MIL-101(Fe), the -NH modification could significantly improve the electronic conductivity of NH-MIL-101(Fe) by enhancing its Fermi level (-4.28 eV) and binding energy to PS (-1.19 eV). The free radical quenching experiments were combined with electron paramagnetic resonance (EPR) confirmed that free radicals (SO, OH, O) worked together with the non-radical (O) reaction to remove 91% BPF within 40 min in the NH-MIL-101(Fe)/PS system. The two proposed BPF degradation pathway were related to hydroxylation, oxidation and ring cracking. The toxicity of the BPF degradation intermediates as well as its final products were also evaluated.

摘要

在这项研究中,使用了两种基于铁的金属有机骨架化合物(MOFs),并将其作为过硫酸盐(PS)激活剂来降解双酚 F(BPF)进行了比较。在不同的反应条件下验证了在催化体系中使用氨基功能化 MOFs 的突出优势,并探讨了其机制。结果表明,NH-MIL-101(Fe)/PS 体系不仅具有较宽的 pH 适用范围,而且对共存阴离子和腐殖酸的干扰具有出色的催化性能。密度泛函理论(DFT)计算表明,与 MIL-101(Fe)相比,-NH 修饰通过提高其费米能级(-4.28 eV)和与 PS 的结合能(-1.19 eV),可以显著提高 NH-MIL-101(Fe)的电子电导率。自由基淬灭实验与电子顺磁共振(EPR)相结合,证实了在 NH-MIL-101(Fe)/PS 体系中,自由基(SO、OH、O)与非自由基(O)一起作用,在 40 分钟内可去除 91%的 BPF。提出了两种与羟化、氧化和环断裂有关的 BPF 降解途径。还评估了 BPF 降解中间产物及其最终产物的毒性。

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