Enhanced Degradation of Micropollutants in a Peracetic Acid-Fe(III) System with Picolinic Acid.

Activation of peracetic acid (PAA) with iron species is an emerging advanced oxidation process (AOP). This study investigates the use of the chelating agent picolinic acid (PICA) to extend the pH range and enhance the performance of the PAA-Fe(III) AOP. Compared to the PAA-Fe(III) system, the PAA-Fe(III)-PICA system degrades various micropollutants (MPs: methylene blue, naproxen, sulfamethoxazole, carbamazepine, trimethoprim, diclofenac, and bisphenol-A) much more rapidly at higher pH, achieving almost complete removal of parent compounds within 10 min. PAA significantly outperforms the coexistent H2O2 and is the key oxidant for rapid compound degradation. Other chelating agents, EDTA, NTA, citric acid, proline, and nicotinic acid, could not enhance MP degradation in the PAA-Fe(III) system, while 2,6-pyridinedicarboxylic acid with a structure similar to PICA moderately enhanced MP degradation. Experiments with scavengers (tert-butyl alcohol and methyl phenyl sulfoxide) and a probe compound (benzoic acid) confirmed that high-valent iron species [Fe(IV) and/or Fe(V)], rather than radicals, are the major reactive species contributing to MP degradation. The oxidation products of methylene blue, naproxen, and sulfamethoxazole by PAA-Fe(III)-PICA were characterized and supported the proposed mechanism. This work demonstrates that PICA is an effective complexing ligand to assist the Fenton reaction of PAA by extending the applicable pH range and accelerating the catalytic ability of Fe(III).

Oxygen activation by mononuclear nonheme iron dioxygenases involved in the degradation of aromatics.

Molecular oxygen is utilized in numerous metabolic pathways fundamental for life. Mononuclear nonheme iron-dependent oxygenase enzymes are well known for their involvement in some of these pathways, activating O2 so that oxygen atoms can be incorporated into their primary substrates. These reactions often initiate pathways that allow organisms to use stable organic molecules as sources of carbon and energy for growth. From the myriad of reactions in which these enzymes are involved, this perspective recounts the general mechanisms of aromatic dihydroxylation and oxidative ring cleavage, both of which are ubiquitous chemical reactions found in life-sustaining processes. The organic substrate provides all four electrons required for oxygen activation and insertion in the reactions mediated by extradiol and intradiol ring-cleaving catechol dioxygenases. In contrast, two of the electrons are provided by NADH in the cis-dihydroxylation mechanism of Rieske dioxygenases. The catalytic nonheme Fe center, with the aid of active site residues, facilitates these electron transfers to O2 as key elements of the activation processes. This review discusses some general questions for the catalytic strategies of oxygen activation and insertion into aromatic compounds employed by mononuclear nonheme iron-dependent dioxygenases. These include: (1) how oxygen is activated, (2) whether there are common intermediates before oxygen transfer to the aromatic substrate, and (3) are these key intermediates unique to mononuclear nonheme iron dioxygenases?

Ferrate (VI) oxidation of sulfamethoxazole enhanced by magnetized sludge-based biochar: Active sites regulation and degradation mechanism analysis.

Developing non radical systems for antibiotic degradation is crucial for addressing the inefficiency of conventional radical systems. In this study, novel magnetic-modified sludge biochar (MASBC) was synthesized to significantly enhance the oxidative degradation of sulfamethoxazole (SMX) by ferrate (Fe (VI)). In the Fe (VI)/MASBC system, 90.46% of SMX at a concentration of 10 µM and 49.34% of the total organic carbon (TOC) could be removed under optimal conditions of 100 µM of Fe (VI) and 0.40 g/L of MASBC within 10 min. Furthermore, the Fe (VI)/MASBC system was demonstrated with broad-spectrum removal capability towards sulfonamides in single or mixture. Quenching experiments, EPR analyses, and electrochemical experiments revealed that direct electron transfer (DET) and •O2- were mainly responsible for the removal of SMX, with functional groups (e.g., -OH, C=O) and Fe-O (redox of Fe (III)/Fe (II)) acting as the active sites, while the probe experiments showed that Fe (IV)/Fe (V) made a minor contribution to the degradation of SMX. Benefiting from the DET, the Fe (VI)/MASBC system exhibited a wide pH adaptation range (e.g., from 5.0 to 10.0) and strong anti-interference ability. The N atoms and their neighboring atoms in SMX were the prior degradation sites, with the cleavage of bond and ring opening. The degradation products showed low or non-toxicity according to ECOSAR program assessment. The removal of SMX remained within a reasonable range of 71.33%-90.46% over five consecutive cycles. Also, the Fe (VI)/MASBC system was demonstrated to be effectively applied for successful SMX removal in various water matrices, including ultrapure water, tap water, lake water, Yangtze River water, and wastewater. Therefore, this study offered new insights into the mechanism of Fe (VI) oxidation and would contribute to the efficient treatment of organic pollutants.

Selective formation of high-valent iron in Fenton-like system for emerging contaminants degradation under near-neutral and high-salt conditions.

In view of the near-neutral and high-salt conditions, the Fenton technology with hydroxyl radicals (HO•) as the main reactive species is difficult to satisfy the removal of trace emerging contaminants (ECs) in pharmaceutical sewage. Here, a layered double hydroxide FeZn-LDH was prepared, and the selective formation of ≡Fe(IV)=O in Fenton-like system was accomplished by the chemical environment regulation of the iron sites and the pH control of the microregion. The introduced zinc can increase the length of Fe-O bond in the FeZn-LDH shell layer by 0.22 Å compared to that in Fe2O3, which was conducive to the oxygen transfer process between ≡Fe(III) and H2O2, resulting in the ≡Fe(IV)=O formation. Besides, the amphoteric hydroxide Zn(OH)2 can regulate the pH of the FeZn-LDH surface microregion, maintaining reaction pH at around 6.5-7.5, which could avoid the quenching of ≡Fe(IV)=O by H+. On the other hand, owing to the anti-interference of ≡Fe(IV)=O and the near-zero Zeta potential on the FeZn-LDH surface, the trace ECs can also be effectively degraded under high-salt conditions. Consequently, the process of ≡Fe(IV)=O generation in FeZn-LDH system can satisfy the efficient removal of ECs under near-neutral and high-salt conditions.

Quantitative probing of reactive oxygen species and their selective degradation on contaminants in peroxymonosulfate-based process enhanced by picolinic acid.

The processes of Fe(III) activated peroxymonosulfate (PMS) in degrading contaminants have been extensively studied. Herein, a biodegradable chelating agent, picolinic acid (PICA), was introduced to the PMS/Fe(III) process to improve the reaction efficiency. The emphases of this study were placed on the quantification of steady-state concentrations of reactive oxygen species (ROS). Experiments presented that five types of ROS, including Fe(IV), SO4•-, HO•, 1O2 and O2•- coexisted in this system. Four typical probe compounds were used to quantify the steady-state concentration of ROS under different variables. The steady-state concentration of Fe(IV) ([Fe(IV)]ss) was 3-5 orders of magnitude higher than that of other ROS, followed by 1O2 and SO4•-, whereas HO• had the lowest concentration. The reaction between PMS and PICA was first explored in our study and results showed that 1O2 and O2•- would form in this reaction. Owing to the hybrid oxidation by multiple ROS, this system showed high oxidation capacity, and could effectively degrade a variety of pollutants. The contributions of ROS to the alleviation of pollutants varied depending on their concentrations and specific reactivity of substrates. Generally, organic contaminants with phenol structures were prone to react with Fe(IV). Overall, this study compared the steady-state concentrations of different ROS and revealed the intrinsic ROS formation mechanisms.

Peroxymonosulfate activated by natural porphyrin derivatives for rapid degradation of organic pollutants via singlet oxygen and high-valent iron-oxo species.

The activation of peroxymonosulfate (PMS) by sodium ferric chlorophyllin (SFC), a natural porphyrin derivative extracted from chlorophyll-rich substances, was systematically investigated for facile degradation of bisphenol A (BPA). SFC/PMS is capable of degrading 97.5% of BPA in the first 10 min with the initial BPA concentration of 20 mg/L and pH = 3, whereas conventional Fe2+/PMS could only remove 22.6% of BPA under identical conditions. It demonstrates a prominent flexibility to a broad pH range of 3-11 with complete pollutant degradation. A remarkable tolerance toward concomitant high concentration of inorganic anions (100 mM) was also observed, among which (bi)carbonates can even accelerate the degradation. The nonradical oxidation species, including high-valent iron-oxo porphyrin species and 1O2, are identified as dominant species. Particularly, the generation and participation of 1O2 in the reaction is evidenced by experimental and theoretical methods, which is vastly different from the previous study. The specific activation mechanism is unveiled by density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The results shed light on effective PMS activation by iron (III) porphyrin and the proposed natural porphyrin derivative would be a promising candidate for efficient abatement of recalcitrant pollutants toward complicated aqueous media in wastewater treatment.

Cooperation of multiple active species generated in hydrogen peroxide activation by iron porphyrin for phenolic pollutants degradation.

The narrow acid pH range and the nonselectivity of the dominant •OH limit the Fenton systems to remediate the organic wastewater. Inspired by the role of heme in physiological processes, we employed iron porphyrin as a novel homogeneous catalyst to address this issue. Multiple active species are identified during the activation of H2O2, including high-valent iron porphyrin ((por)Fe(IV)) species ((por)Fe(IV)-OH, (por)+•Fe(IV)=O) and oxygen-centered radicals (•OH, HO2•/•O2-), as well as atomic hydrogen (*H) and carbon-centered radicals. With the cooperation of these active species, the degradation of pollutants could be resistant to the interference of concomitant ions and proceed over a wide pH range. This cooperative behavior is further verified by intermediates identified from bisphenol A degradation. Specifically, the presence of *H could facilitate the cleavage of the C-C bond and the addition of unsaturated or aromatic molecules. (Por)+•Fe(IV)=O could hydroxylate substrates with an oxygen rebound mechanism. Hydrogen atom abstraction of contaminants could be performed by (por)Fe(IV)-OH to form desaturated products by attacking oxygen-centered radicals. The ecotoxicity of bisphenol A could be significantly decreased through degradation. This study would provide a new approach to wastewater treatment and shed light on the interaction between metalloporphyrin and peroxide in an aqueous solution.

Recent advances in metalloporphyrins for environmental and energy applications.

Porphyrin-based chemistry has reached an unprecedented period of rapid development after decades of study. Due to attractive multifunctional properties, porphyrins and their analogues have emerged as multifunctional organometals for environmental and energy purposes. In particular, pioneer works have been conducted to explore their application in pollution abatement, energy conversion and storage and molecule recognition. This review summarizes recent advances of porphyrins chemistry, focusing on elucidating the nature of catalytic process. The Fenton-like redox chemistry and photo-excitability of porphyrins and their analogues are discussed, highlighting the generation of high-valent iron oxo porphyrin species. Finally, challenges in current research are identified and perspectives for future development in this area are presented.