Generation of Iron(IV) in the Oxidation of Amines by Ferrate(VI): Theoretical Insight and Implications in Oxidizing Pharmaceuticals

Baum, J. Clayton; Feng, Mingbao; Guo, Binglin; Huang, Ching-Hua; Sharma, Virender K.

doi:10.1021/acsestwater.1c00156

Cited by 14 publications

(13 citation statements)

References 58 publications

(95 reference statements)

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“…More recently, the activation of Fe VI O 4 2– by typical aliphatic amines (i.e., monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA)) was demonstrated using TMP as a model pollutant. The superior performance of these oxidation systems was ascribed to the generation of highly reactive Fe IV species …”

Section: Activation Of Ferrate(vi)mentioning

confidence: 99%

Reactive High-Valent Iron Intermediates in Enhancing Treatment of Water by Ferrate

Sharma

Feng

Dionysiou

et al. 2021

Environ. Sci. Technol.

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Efforts are being made to tune the reactivity of the tetraoxy anion of iron in the +6 oxidation state (FeVIO4 2–), commonly called ferrate, to further enhance its applications in various environmental fields. This review critically examines the strategies to generate highly reactive high-valent iron intermediates, FeVO4 3– (FeV) and FeIVO4 4– or FeIVO3 2– (FeIV) species, from FeVIO4 2–, for the treatment of polluted water with greater efficiency. Approaches to produce FeV and FeIV species from FeVIO4 2– include additions of acid (e.g., HCl), metal ions (e.g., Fe(III)), and reductants (R). Details on applying various inorganic reductants (R) to generate FeV and FeIV from FeVIO4 2– via initial single electron-transfer (SET) and oxygen-atom transfer (OAT) to oxidize recalcitrant pollutants are presented. The common constituents of urine (e.g., carbonate, ammonia, and creatinine) and different solids (e.g., silica and hydrochar) were found to accelerate the oxidation of pharmaceuticals by FeVIO4 2–, with potential mechanisms provided. The challenges of providing direct evidence of the formation of FeV/FeIV species are discussed. Kinetic modeling and density functional theory (DFT) calculations provide opportunities to distinguish between the two intermediates (i.e., FeIV and FeV) in order to enhance oxidation reactions utilizing FeVIO4 2–. Further mechanistic elucidation of activated ferrate systems is vital to achieve high efficiency in oxidizing emerging pollutants in various aqueous streams.

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Section: Activation Of Ferrate(vi)mentioning

confidence: 99%

Reactive High-Valent Iron Intermediates in Enhancing Treatment of Water by Ferrate

Sharma

Feng

Dionysiou

et al. 2021

Environ. Sci. Technol.

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“…Ferrate(VI) [Fe(VI), HFeO 4 – /FeO 4 2– ] − and peracetic acid [PAA, CH 3 C(O)OOH] , are two promising alternative oxidants that are attracting growing interest from environmental engineers and scientists due to their great capacity for pathogen inactivation − and micropollutant abatement. ,− Nonetheless, ferrate(VI) and PAA both undergo self-decay under environmentally relevant conditions, and their reactivity toward certain contaminants is limited. ,− Thus, various methods for enhancing the oxidation ability of PAA and ferrate(VI) have been developed in recent years. For example, UV, , Fe(II), Fe(III)-picolinic acid-, Co(II), − Ru(III), MoS 2 , and Co-based catalysts − have been developed to activate PAA.…”

Section: Introductionmentioning

confidence: 99%

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

Wang

Kim

Ashley

et al. 2022

Environ. Sci. Technol.

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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 radicalshad negligible contribution. Second, we removed the coexistent hydrogen peroxide (H 2 O 2 ) 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 M −1 s −1 while that of H 2 O 2 was as high as (2.01 ± 0.12) × 10 1 M −1 s −1 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 highvalent metals and organic contaminants and confirms the benefits of co-application of ferrate(VI) and PAA for alkaline wastewater treatment.

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“…The reactivities of Cr(IV) and Cr(V) have been examined by studying the oxidation of different organic compounds (e.g., carbohydrates, alcohols, thiols, amino acids, and peptides) by Cr(VI). Both Cr(IV) and Cr(V) can oxidize compounds (X) by either a one-electron pathway to form a radical (X • ) or a two-electron pathway to form an oxidized product (X(O)) (eqs –). ,,− Therefore, different mechanisms may occur, depending on the concentrations of the chromium species and X. Cr(IV) and Cr(V) may form complex species with compounds (e.g., carbohydrates and peptides) to increase their stabilization, similar to high-valent iron species like ferrates. , These complexes can possibly react with organic compounds as well. , The role of Cr(IV) and Cr(V) in the degradation of organic pollutants in water is further described below.…”

Section: Chromium(v) and Chromium(iv) Speciesmentioning

confidence: 99%

“…4,5 Among heavy metals, chromium (Cr) is a major pollutant, entering soil from wastes of industrial activities such as coal-fired power generation, chrome pigment production, wood preservation, stainless steel production, galvanization, cement production, electroplating, and leather tanning. 6−9 Chromium has four isotopes in nature: isotopes 50 Cr, 52 Cr, 53 Cr, and 54 Cr with respective abundances of 4.35%, 83.79%, 9.50%, and 2.36%. 10 The oxidation states of chromium range from −2 to +6.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Cr(IV) and Cr(V) may form complex species with compounds (e.g., carbohydrates and peptides) to increase their stabilization, 50 similar to high-valent iron species like ferrates. 51,52 These complexes can possibly react with organic compounds as well. 48,50 The role of Cr(IV) and Cr(V) in the degradation of organic pollutants in water is further described below.…”

Section: ■ Introductionmentioning

confidence: 99%

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Overlooked Role of Chromium(V) and Chromium(IV) in Chromium Redox Reactions of Environmental Importance

Bell

McDonald

et al. 2022

ACS EST Water

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Chromium (Cr) is a well-known heavy metal contaminant with toxicity highly dependent on its oxidation state. Hexavalent Cr (Cr(VI)) is a known carcinogen while trivalent chromium (Cr(III)) is significantly less toxic. The reduction of Cr(VI) and oxidation of Cr(III) in different compartments of the environment occur through intermediate species pentavalent Cr (Cr(V)) and tetravalent Cr (Cr(IV)), which are highly reactive. The environmental literature generally lacks information on Cr(V) and Cr(IV) species in various redox processes. This Perspective presents the aquatic chemistry of Cr(V) and Cr(IV), which includes their spectroscopic characterizations and kinetic behaviors under different environmental conditions. Examples are presented to demonstrate the possible existence of the intermediate Cr species in different systems of environmental importance such as the reduction of Cr(VI) by iron(II) (Fe(II)), molecules of natural organic matter (e.g., fulvic acids and carboxylic acids), and oxidation of Cr(III) by hydrogen peroxide, hypochlorite, and manganese oxides (MnO x ). The oxidation of organic pollutants by the Cr(VI)–S(IV) system is also discussed. This Perspective suggests in-depth investigations on the redox reactions of Cr relevant to environmental processes to shed light on the mechanisms of the generation of Cr(V) and Cr(IV) species and their roles in water decontamination.

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Generation of Iron(IV) in the Oxidation of Amines by Ferrate(VI): Theoretical Insight and Implications in Oxidizing Pharmaceuticals

Cited by 14 publications

References 58 publications

Reactive High-Valent Iron Intermediates in Enhancing Treatment of Water by Ferrate

Reactive High-Valent Iron Intermediates in Enhancing Treatment of Water by Ferrate

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

Overlooked Role of Chromium(V) and Chromium(IV) in Chromium Redox Reactions of Environmental Importance

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