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可见光 LED 下 Fe(III)浸渍 N 掺杂 TiO2 双组分光催化剂促进氧单硫酸盐活化降解克百威的研究进展

Insights into peroxymonosulfate activation for carbofuran degradation under visible LED via a double-component photocatalyst of Fe (III) impregnated N-doped TiO.

机构信息

Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong.

Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong.

出版信息

Chemosphere. 2019 Dec;237:124487. doi: 10.1016/j.chemosphere.2019.124487. Epub 2019 Jul 31.

Abstract

A hybrid process was proposed for carbofuran (CBF) degradation, a carbamate pesticide with a special refractory property, through peroxymonosulfate (PMS) activation under visible LED (Vis LED) by Fe impregnated N-doped TiO photocatalyst (FeNT). An in-depth investigation was conducted to examine the synergistic effect of the FeNT/PMS/Vis LED process under various reaction conditions. An increase in the rate constant was observed with the increment of pH from 2.4 to 7.4, implying the feasibility of the process at neutral pH. A further increase in pH from 8.9 to 11 showed a sudden drop in the rate constant (if the role of base activation is ignored). The efficiency of CBF degradation is still more than 70% after adding NO, SO, HCO, and Cl. Interestingly, the efficiency was not influenced even after the further increment of nitrate concentration. Furthermore, the high chloride concentrations caused an enhanced efficiency due to the generation of reactive halogens through two-electron transfer. Sixteen major intermediates were recognized and eight of them were never reported in the previous studies. Surprisingly, a new degradation pathway was noted in this study via H-abstractions and cyclization mechanisms. The FeNT/PMS/Vis LED process exhibited a dual functionality in terms of mineralization efficiency and about 90% TOC reduction can be achieved. Therefore, these findings provide new insights into the mechanism of PMS activation under Vis LED after coupling non-metal doped TiO photocatalyst with a metal component, and its implications for degradation of refractory and non-biodegradable pollutants in wastewater.

摘要

提出了一种通过负载铁的氮掺杂 TiO2 光催化剂(FeNT)可见光 LED(Vis LED)下过一硫酸盐(PMS)活化来降解具有特殊难降解性质的氨基甲酸酯类农药克百威(CBF)的杂化工艺。在不同反应条件下,深入研究了 FeNT/PMS/Vis LED 工艺的协同效应。随着 pH 值从 2.4 增加到 7.4,速率常数增加,表明该过程在中性 pH 值下是可行的。进一步将 pH 值从 8.9 增加到 11 时,速率常数突然下降(如果忽略碱活化的作用)。即使在进一步增加硝酸盐浓度的情况下,CBF 的降解效率仍超过 70%。此外,添加 NO、SO、HCO 和 Cl 后,降解效率仍保持在 70%以上。有趣的是,即使硝酸盐浓度进一步增加,效率也不受影响。此外,高氯浓度由于通过两电子转移生成活性卤素来提高了效率。鉴定出 16 种主要中间体,其中 8 种在以前的研究中从未报道过。令人惊讶的是,本研究通过 H 提取和环化机制注意到了一种新的降解途径。FeNT/PMS/Vis LED 工艺在矿化效率方面表现出双重功能,TOC 去除率约为 90%。因此,这些发现为非金属掺杂 TiO2 光催化剂与金属成分结合后 Vis LED 下 PMS 活化的机制提供了新的见解,并对废水难降解和不可生物降解污染物的降解具有重要意义。

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