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水热合成FeS₂作为一种高效芬顿试剂通过超氧化物介导的Fe(II)/Fe(III)循环降解甲草胺

Hydrothermal Synthesis of FeS2 as a High-Efficiency Fenton Reagent to Degrade Alachlor via Superoxide-Mediated Fe(II)/Fe(III) Cycle.

作者信息

Liu Wei, Wang Yueyao, Ai Zhihui, Zhang Lizhi

机构信息

Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental Chemistry, Central China Normal University , Wuhan 430079, PR China.

出版信息

ACS Appl Mater Interfaces. 2015 Dec 30;7(51):28534-44. doi: 10.1021/acsami.5b09919. Epub 2015 Dec 18.

Abstract

In this study, we demonstrate that hydrothermally synthesized FeS2 (syn-FeS2) is highly efficient at catalyzing the H2O2 decomposition for alachlor degradation at a wide range of initial pH (3.2-9.2). The alachlor degradation rate of syn-FeS2 heterogeneous Fenton system was almost 55 times that of its commercial pyrite (com-FeS2) counterpart at an initial pH of 6.2. Experimental results revealed that the alachlor oxidation enhancement in the syn-FeS2 Fenton system was attributed to the molecular oxygen activation induced by more surface-bound ferrous ions on syn-FeS2. The molecular oxygen activation process could generate superoxide anions to accelerate the Fe(II)/Fe(III) cycle on the syn-FeS2 surface, which favored the H2O2 decomposition to generate more hydroxyl radicals for the alachlor oxidation. It was found that the hydroxyl radicals generation rate constant of syn-FeS2 Fenton system was 71 times that of its com-FeS2 counterpart, and even 1-3 orders of magnitude larger than those of commonly used Fe-bearing heterogeneous catalysts. We detected the alachlor degradation intermediates with gas chromatography-mass spectrometry to propose tentatively a possible alachlor degradation pathway. These interesting findings could provide some new insights on the molecular oxygen activation induced by FeS2 minerals and the subsequent heterogeneous Fenton degradation of organic pollutants in the environment.

摘要

在本研究中,我们证明水热合成的FeS₂(合成FeS₂)在很宽的初始pH范围(3.2 - 9.2)内,对催化H₂O₂分解以降解甲草胺具有高效性。在初始pH为6.2时,合成FeS₂非均相芬顿体系中甲草胺的降解速率几乎是其商业黄铁矿(商业FeS₂)对应体系的55倍。实验结果表明,合成FeS₂芬顿体系中甲草胺氧化增强归因于合成FeS₂上更多表面结合的亚铁离子诱导的分子氧活化。分子氧活化过程可产生超氧阴离子,以加速合成FeS₂表面的Fe(II)/Fe(III)循环,这有利于H₂O₂分解产生更多的羟基自由基用于甲草胺氧化。发现合成FeS₂芬顿体系的羟基自由基生成速率常数是其商业FeS₂对应体系的71倍,甚至比常用的含铁非均相催化剂的速率常数大1 - 3个数量级。我们用气相色谱 - 质谱联用仪检测了甲草胺降解中间体,初步提出了一条可能的甲草胺降解途径。这些有趣的发现可为FeS₂矿物诱导的分子氧活化以及环境中有机污染物随后的非均相芬顿降解提供一些新的见解。

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