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过氧乙酸通过提高电子转移效率增强高铁酸盐(VI)对微量污染物的降解。

Peracetic Acid Enhances Micropollutant Degradation by Ferrate(VI) through Promotion of Electron Transfer Efficiency.

机构信息

School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States.

Department of Chemistry and Biochemistry, Spelman College, Atlanta, Georgia 30314, United States.

出版信息

Environ Sci Technol. 2022 Aug 16;56(16):11683-11693. doi: 10.1021/acs.est.2c02381. Epub 2022 Jul 26.

DOI:10.1021/acs.est.2c02381
PMID:35880779
Abstract

Ferrate(VI) and peracetic acid (PAA) are two oxidants of growing importance in water treatment. Recently, our group found that simultaneous application of ferrate(VI) and PAA led to much faster degradation of micropollutants compared to that by a single oxidant, and this paper systematically evaluated the underlying mechanisms. First, we used benzoic acid and methyl phenyl sulfoxide as probe compounds and concluded that Fe(IV)/Fe(V) was the main reactive species, while organic radicals [CHC(O)O/CHC(O)OO] had negligible contribution. Second, we removed the coexistent hydrogen peroxide (HO) in PAA stock solution with free chlorine and, to our surprise, found the second-order reaction rate constant between ferrate(VI) and PAA to be only about 1.44 ± 0.12 Ms while that of HO was as high as (2.01 ± 0.12) × 10 Ms at pH 9.0. Finally, further experiments on ferrate(VI)-bisulfite and ferrate(VI)-2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic)acid systems confirmed that PAA was not an activator for ferrate(VI). Rather, PAA could enhance the oxidation capacity of Fe(IV)/Fe(V), making their oxidation outcompete self-decay. This study, for the first time, reveals the ability of PAA to promote electron transfer efficiency between high-valent metals and organic contaminants and confirms the benefits of co-application of ferrate(VI) and PAA for alkaline wastewater treatment.

摘要

高铁酸盐(VI)和过氧乙酸(PAA)是水处理中两种越来越重要的氧化剂。最近,我们小组发现,与单一氧化剂相比,同时应用高铁酸盐(VI)和过氧乙酸会导致污染物更快地降解,本文系统地评估了其潜在的机制。首先,我们使用苯甲酸和甲基苯基亚砜作为探针化合物,得出 Fe(IV)/Fe(V)是主要的反应性物质,而有机自由基[CHC(O)O/CHC(O)OO]的贡献可以忽略不计。其次,我们用游离氯去除过氧乙酸储备溶液中共存的过氧化氢(HO),令我们惊讶的是,发现高铁酸盐(VI)和过氧乙酸之间的二级反应速率常数仅约为 1.44 ± 0.12 Ms,而 HO 的反应速率常数高达(2.01 ± 0.12)×10 Ms,pH 值为 9.0。最后,在高铁酸盐(VI)-亚硫酸氢盐和高铁酸盐(VI)-2,2'-联氮-双(3-乙基苯并噻唑啉-6-磺酸)体系中的进一步实验证实,过氧乙酸不是高铁酸盐(VI)的活化剂。相反,过氧乙酸可以增强 Fe(IV)/Fe(V)的氧化能力,使其氧化能力超过自身衰减。本研究首次揭示了过氧乙酸促进高价金属与有机污染物之间电子转移效率的能力,并证实了高铁酸盐(VI)和过氧乙酸共应用于碱性废水处理的益处。

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