New Insight into a Fenton-like Reaction Mechanism over Sulfidated β-FeOOH: Key Role of Sulfidation in Efficient Iron(III) Reduction and Sulfate Radical Generation

IF 11.3 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL
Xike Tian, Tiantian Luo, Yulun Nie*, Jianbo Shi, Yayang Tian, Dionysios D. Dionysiou and Yanxin Wang, 
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引用次数: 32

Abstract

Sulfidation can greatly improve the efficiency of utilization of reducing equivalents for contaminant removal; however, whether this method benefits Fenton-like reactions or not and the possible mechanism are not well understood. In this study, we revealed that surface sulfidation can greatly promote the heterogeneous Fenton activity of β-FeOOH (Fe3S4@β-FeOOH) by 40 times, in which not only the OH formation was enhanced but also SO4•– as a new oxidation species was generated. Moreover, their contribution to metronidazole (MTZ) degradation was 52.5 and 37.1%, respectively. In comparison, almost no HO2/O2•– was detected in the Fe3S4@β-FeOOH/H2O2 system. These results were different from some previously reported Fenton counterparts. Based on the characterization and probe experiments, sulfur species, including S2–, S0, and Sn2–, as an electron donor and electron shuttle were responsible for efficient conversion of Fe(III) into Fe(II) other than via the Haber–Weiss mechanism, leading to excellent OH generation via a Fenton-like mechanism. Most importantly, HSO5 can be generated from SO32– oxidized by OH, and its scission into SO4•– was not dependent on the extra electric potential or Fe–O2–S(IV) intermediate. These findings provided new insight for utilizing sulfidation to improve the activity of iron-based Fenton catalysts.

Abstract Image

磺化β-FeOOH Fenton-like反应机理的新认识:磺化在铁(III)高效还原和硫酸盐自由基生成中的关键作用
硫化可大大提高还原性当量的利用效率;然而,这种方法是否有利于类芬顿反应以及可能的机制尚不清楚。本研究发现,表面硫化可使β-FeOOH (Fe3S4@β-FeOOH)的非均相Fenton活性提高40倍,不仅增强了•OH的生成,还生成了新的氧化物质SO4•-。此外,它们对甲硝唑(MTZ)降解的贡献率分别为52.5%和37.1%。相比之下,Fe3S4@β-FeOOH/H2O2体系中几乎没有检测到HO2•/O2•-。这些结果与之前报道的一些芬顿实验结果不同。基于表征和探针实验,包括S2 -、S0和Sn2 -在内的硫种作为电子供体和电子穿梭体,除了通过Haber-Weiss机制外,还能有效地将Fe(III)转化为Fe(II),从而通过Fenton-like机制生成出色的•OH。最重要的是,HSO5 -可以由•OH氧化的SO32 -生成,并且其裂解成SO4•-不依赖于额外的电势或Fe-O2-S (IV)中间体。这些发现为利用硫化作用提高铁基Fenton催化剂的活性提供了新的思路。
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来源期刊
环境科学与技术
环境科学与技术 环境科学-工程:环境
CiteScore
17.50
自引率
9.60%
发文量
12359
审稿时长
2.8 months
期刊介绍: Environmental Science & Technology (ES&T) is a co-sponsored academic and technical magazine by the Hubei Provincial Environmental Protection Bureau and the Hubei Provincial Academy of Environmental Sciences. Environmental Science & Technology (ES&T) holds the status of Chinese core journals, scientific papers source journals of China, Chinese Science Citation Database source journals, and Chinese Academic Journal Comprehensive Evaluation Database source journals. This publication focuses on the academic field of environmental protection, featuring articles related to environmental protection and technical advancements.
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