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阐明过一硫酸盐活化催化氧化磺胺甲恶唑过程中的计量效率、自由基生成和转化途径。

Elucidation of stoichiometric efficiency, radical generation and transformation pathway during catalytic oxidation of sulfamethoxazole via peroxymonosulfate activation.

机构信息

Interdisciplinary Graduate School, Nanyang Technological University, 637141, Singapore; Nanyang Environment and Water Research Institute, Nanyang Technological University, 637141, Singapore.

Nanyang Environment and Water Research Institute, Nanyang Technological University, 637141, Singapore; School of Chemical Sciences, Universiti Sains Malaysia, 11800, Penang, Malaysia.

出版信息

Water Res. 2019 Mar 15;151:64-74. doi: 10.1016/j.watres.2018.12.007. Epub 2018 Dec 15.

DOI:10.1016/j.watres.2018.12.007
PMID:30594091
Abstract

In this work, nano-bimetallic Co/Fe oxides with different stoichiometric Co/Fe ratios were prepared using a novel one-step solution combustion method. The nano-bimetallic Co/Fe oxides were used for sulfamethoxazole (SMX) degradation via peroxymonosulfate (PMS) activation. The stoichiometric efficiencies of the as-prepared nano-bimetallic catalysts were calculated and compared for the first time. The radical generation was identified by electron paramagnetic resonance (EPR) as well as chemical quenching experiments, in which different scavengers were used and compared. The catalytic PMS activation mechanism in the presence of catalyst was examined by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results showed that besides SO• and •OH, •OOH was also detected in the PMS/CoFeO system. Meanwhile, in addition to the previously proposed radical oxidation pathway, the results showed that SMX degradation also involved a non-radical oxidation, which could be verified by the degradation experiment without catalyst as well as the detection of O. In the PMS activation process, cobalt functioned as the active site on CoFeO while Fe oxide functioned as the adsorption site. The electron transfer mechanism was proposed based on the XPS and metal leaching results. Additionally, via the detection of transformation products, different SMX transformation pathways involving nitration, hydroxylation and hydrolysis in the PMS/CoFeO system were proposed.

摘要

在这项工作中,采用一种新颖的一步溶液燃烧法制备了具有不同化学计量比 Co/Fe 的纳米双金属 Co/Fe 氧化物。纳米双金属 Co/Fe 氧化物用于过一硫酸盐 (PMS) 活化降解磺胺甲恶唑 (SMX)。首次计算并比较了所制备的纳米双金属催化剂的化学计量效率。通过电子顺磁共振 (EPR) 和化学猝灭实验确定了自由基的生成,其中使用了不同的猝灭剂并进行了比较。通过傅里叶变换红外光谱 (FTIR) 和 X 射线光电子能谱 (XPS) 研究了催化剂存在时的催化 PMS 活化机制。结果表明,除了 SO•和 •OH,在 PMS/CoFeO 体系中还检测到了 •OOH。同时,除了先前提出的自由基氧化途径外,结果表明 SMX 降解还涉及非自由基氧化,这可以通过没有催化剂的降解实验以及 O 的检测来验证。在 PMS 活化过程中,Co 在 CoFeO 中充当活性位点,而 Fe 氧化物充当吸附位点。基于 XPS 和金属浸出结果提出了电子转移机制。此外,通过检测转化产物,提出了 PMS/CoFeO 体系中涉及硝化、羟化和水解的不同 SMX 转化途径。

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