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纳米级LaFeCuO钙钛矿活化过一硫酸盐强化降解阿特拉津:性能与机制

Enhanced degradation of atrazine by nanoscale LaFeCuO perovskite activated peroxymonosulfate: Performance and mechanism.

作者信息

Wang Guoying, Cheng Cheng, Zhu Jianchao, Wang Lijun, Gao Shengwang, Xia Xunfeng

机构信息

College of Environmental Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, PR China.

College of Environmental Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, PR China; Research Center for Rural Environmental Protection, Chinese Research Academy of Environmental Sciences, Beijing 100012, PR China.

出版信息

Sci Total Environ. 2019 Jul 10;673:565-575. doi: 10.1016/j.scitotenv.2019.04.098. Epub 2019 Apr 10.

Abstract

Cu-doped LaFeO perovskite (LaFeCuO, LFC) synthesized using a sol-gel method was introduced in the heterogeneous activation of peroxymonosulfate (PMS) for atrazine degradation. The obtained LFC catalysts were characterized by several technologies and the results showed that Cu was incorporated into the perovskites lattice successfully. In addition, the introduction of Cu resulted in the mixed valence state of Fe(III)/Fe(II) and Cu(II)/Cu(I) in perovskite structure. LaFeCuO (LFC) exhibited excellent catalytic activity and stability towards the degradation of atrazine. Atrazine (23 μM) was removed completely within 60 min in the presence of 0.5 g/L catalyst and 0.5 mM PMS. The efficient degradation was obtained when the initial pH ranged from 2 to 10. Sulfate radicals (SO) and hydroxyl radicals (HO) generated during activation process were determined as the main reactive species based on the electron spin resonance (ESR) studies and radical quenching experiments. The enhanced catalytic activity derived from the lower valence state of Fe and Cu as well as the synergetic effect between them. A surface catalyzed-redox cycle between Fe(III)/Fe(II) and Cu(II)/Cu(I), along with surface hydroxyl groups (-OH), were all responsible for the decomposition of PMS. The oxygen vacancies could promote the chemical bonding with PMS and enhance the reactivity of Fe and Cu. The 12 transformation products were determined by LC-MS and the degradation mechanisms were further proposed, which involved five different pathways. The perovskite that possesses bimetallic active sites can be a promising catalyst for PMS activation towards the degradation of persistent organic pollutants with high-efficiency.

摘要

采用溶胶 - 凝胶法合成的铜掺杂钙钛矿型LaFeO(LaFeCuO,LFC)被用于过一硫酸盐(PMS)的非均相活化以降解阿特拉津。通过多种技术对所得的LFC催化剂进行了表征,结果表明铜成功地掺入到了钙钛矿晶格中。此外,铜的引入导致了钙钛矿结构中Fe(III)/Fe(II)和Cu(II)/Cu(I)的混合价态。LaFeCuO(LFC)对阿特拉津的降解表现出优异的催化活性和稳定性。在0.5 g/L催化剂和0.5 mM PMS存在的情况下,23 μM的阿特拉津在60分钟内被完全去除。当初始pH值在2至10范围内时,可实现高效降解。基于电子自旋共振(ESR)研究和自由基猝灭实验,确定活化过程中产生的硫酸根自由基(SO)和羟基自由基(HO)为主要的活性物种。增强的催化活性源于Fe和Cu的低价态以及它们之间的协同效应。Fe(III)/Fe(II)和Cu(II)/Cu(I)之间的表面催化氧化还原循环以及表面羟基(-OH)均对PMS的分解起作用。氧空位可促进与PMS的化学键合并增强Fe和Cu的反应性。通过LC-MS确定了12种转化产物,并进一步提出了降解机制,其中涉及五种不同的途径。具有双金属活性位点的钙钛矿有望成为一种高效活化PMS以降解持久性有机污染物的催化剂。

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