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ZnO/ZnMn O 催化过一硫酸盐降解 2,4-二氯苯酚。

Degradation of 2, 4-dichlorophenol by peroxymonosulfate catalyzed by ZnO/ZnMn O.

机构信息

School of Environment Engineering, Wuhan Textile University, Wuhan, China.

Research Center for Clean Production of Textile Dyeing and Printing, Ministry of Education, Wuhan Textile University, Wuhan, China.

出版信息

Water Environ Res. 2024 Feb;96(2):e10984. doi: 10.1002/wer.10984.

Abstract

In this study, a highly efficient peroxymonosulfate (PMS) activator, ZnO/ZnMn O , was synthesized using a simple one-step hydrothermal method. The resulting bimetallic oxide catalyst demonstrated a homogenous and high-purity composition, showcasing synergistic catalytic activity in activating PMS for degrading 2, 4-dichlorophenol (2, 4-DCP) in aqueous solution. This catalytic performance surpassed that of individual ZnO, Mn O , and ZnMn O metal materials. Under the optimized conditions, the removal efficiency of 2, 4-DCP reached approximately 86% within 60 min, and the catalytic ability remained almost constant even after four cycles of recycling. The developed degradation system proved effective in degrading other azo-dye pollutants. Certain inorganic anions such as HPO , HCO , and NO significantly inhibited the degradation of 2, 4-DCP, while Cl and SO did not exhibit such interference. Results from electrochemical experiments indicated that the electron transfer ability of ZnO/ZnMn O surpassed that of individual metals, and electron transfer occurred between ZnO/ZnMn O and the oxidant. The primary active radicals responsible for degrading 2, 4-DCP were identified as SO , OH and O , generated through the oxidation and reduction of PMS catalyzed by Zn (II) and Mn (III). Furthermore, X-ray photoelectron spectroscopy (XPS) analysis of the fresh and used catalysts revealed that the exceptional electron transfer ability of ZnO facilitated the valence transfer of Mn (III) and the transfer of electrons to the catalyst's oxygen surface, thus enhancing the catalytic efficiency. The analysis of radicals and intermediates indicates that the two main pathways for degrading 2, 4-DCP involve hydroxylation and radical attack on its aromatic ring. PRACTITIONER POINTS: A bimetallic ZnO/ZnMn O catalyst was synthesized and characterized. ZnO/ZnMn O can synergistically activate PMS to degrade 2, 4-DCP compared with single metal oxide. Three primary active radicals, O , OH, and SO , were generated to promote the degradation. ZnO promoted electron transfer among the three species of Mn to facilitate oxidizing pollutants. Hydroxylation and radical attack on the aromatic ring of 2, 4-DCP are the two degradation pathways.

摘要

在这项研究中,我们使用一种简单的一步水热法合成了一种高效的过一硫酸盐(PMS)活化剂 ZnO/ZnMn O。所得的双金属氧化物催化剂表现出均匀且高纯度的组成,在活化 PMS 降解水溶液中的 2,4-二氯苯酚(2,4-DCP)方面表现出协同催化活性。这种催化性能超过了单独的 ZnO、Mn O 和 ZnMn O 金属材料。在优化条件下,2,4-DCP 的去除效率在 60 分钟内达到约 86%,并且即使经过四次循环回收,催化能力几乎保持不变。所开发的降解系统在降解其他偶氮染料污染物方面表现出有效性。某些无机阴离子,如 HPO 、HCO 和 NO ,显著抑制了 2,4-DCP 的降解,而 Cl 和 SO 则没有表现出这种干扰。电化学实验结果表明,ZnO/ZnMn O 的电子转移能力超过了单个金属,并且电子在 ZnO/ZnMn O 和氧化剂之间发生转移。负责降解 2,4-DCP 的主要活性自由基被确定为 SO 、OH 和 O ,它们是通过 PMS 在 Zn(II)和 Mn(III)催化下的氧化和还原产生的。此外,对新鲜和使用过的催化剂进行 X 射线光电子能谱(XPS)分析表明,ZnO 的优异电子转移能力促进了 Mn(III)的价转移和电子向催化剂氧表面的转移,从而提高了催化效率。自由基和中间体的分析表明,降解 2,4-DCP 的两个主要途径涉及其芳环的羟化和自由基攻击。

从业者要点

  • 合成并表征了一种双金属 ZnO/ZnMn O 催化剂。

  • ZnO/ZnMn O 可以与单金属氧化物相比,协同激活 PMS 来降解 2,4-DCP。

  • 生成了三种主要的活性自由基 O 、OH 和 SO ,以促进污染物的降解。

  • ZnO 促进了三种 Mn 物种之间的电子转移,有利于氧化污染物。

  • 2,4-DCP 的两种降解途径是芳环的羟化和自由基攻击。

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