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具有强给电子性质的亚铁金属有机框架用于过硫酸盐活化以有效降解水中的磺胺甲恶唑。

Ferrous metal-organic frameworks with strong electron-donating properties for persulfate activation to effectively degrade aqueous sulfamethoxazole.

作者信息

Pu Mengjie, Niu Junfeng, Brusseau Mark L, Sun Yanlong, Zhou Chengzhi, Deng Sheng, Wan Jinquan

机构信息

Research Center for Eco-Environmental Engineering, Dongguan University of Technology, Dongguan, 523808, China.

Department of Soil, Water and Environmental Science, School of Earth and Environmental Sciences, University of Arizona, Tucson, Arizona, 85721, USA.

出版信息

Chem Eng J. 2020 Aug 15;394. doi: 10.1016/j.cej.2020.125044. Epub 2020 Apr 11.

Abstract

Three novel persulfate activators, Fe(II)-based metal-organic frameworks (MOFs) were synthesized for the degradation of sulfamethoxazole (SMX). The degradation experiment results showed that all the Fe(II)MOFs could effectively activate persulfate and degrade more than 97% SMX within 180 min, with higher than 77% persulfate decomposition efficiencies. It was found by Mössbauer spectra that the variation of organic ligands for synthesis have an influence on the content of Fe(II) of these MOFs, thus resulted in the order of activation capacities: Fe(Nic) > Fe(PyBDC) > Fe(PIP). It was demonstrated that the activation of persulfate was mainly ascribed to the heterogeneous process that accomplished by surface-bounded Fe(II) acted as the main active site to provided electrons for persulfate or dissolved oxygen. EPR and molecular probe studies confirmed the coexistence of SO·, ·OH, and O·, and differentiated their contributions in SMX degradation. Possible degradation pathways of SMX were proposed based on the detection results of intermediates by UPLC-MS/MS. This work provides a new prospect into the synthesis of high-performance MOFs with strong electron-donating properties as efficient persulfate activators, which may encourage the employ of MOFs in the wastewater treatment process.

摘要

合成了三种新型过硫酸盐活化剂——基于Fe(II)的金属有机框架材料(MOFs),用于降解磺胺甲恶唑(SMX)。降解实验结果表明,所有Fe(II)MOFs均能有效活化过硫酸盐,在180分钟内降解超过97%的SMX,过硫酸盐分解效率高于77%。通过穆斯堡尔谱发现,合成时有机配体的变化会影响这些MOFs中Fe(II)的含量,从而导致活化能力顺序为:Fe(Nic) > Fe(PyBDC) > Fe(PIP)。结果表明,过硫酸盐的活化主要归因于非均相过程,该过程由表面结合的Fe(II)作为主要活性位点为过硫酸盐或溶解氧提供电子来完成。电子顺磁共振(EPR)和分子探针研究证实了SO·、·OH和O·的共存,并区分了它们在SMX降解中的贡献。基于超高效液相色谱-串联质谱(UPLC-MS/MS)对中间体的检测结果,提出了SMX可能的降解途径。这项工作为合成具有强供电子性能的高性能MOFs作为高效过硫酸盐活化剂提供了新的前景,这可能会促进MOFs在废水处理过程中的应用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5f1a/7785090/ff746dbcbbc1/nihms-1640479-f0001.jpg

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