Persulfate-based Advanced Oxidation Processes Research Articles

Atomically Dispersed Cobalt Anchored on Hollow Tubular Carbon Nitride Mediates Direct Electron Transfer and Oxygen-Related Active Species Path for Activation of Permonosulfate.

Atomically dispersed catalysts anchored on nitrogen-rich substrates present promising application potential for the persulfate-based advanced oxidation process. Nevertheless, efficient activation efficiency and a clear activated mechanism of persulfate remain challenging in carbon nitride-based single-atom catalysts (SACs). To these, combined with the regulation strategy of metal-ligand section and carrier's architecture, an atomically dispersed Co single-atom catalyst anchored on regular hollow tubular carbon nitride (Co/TCN SAC) herein was devised and utilized to activate permonosulfate. As a result, Co/TCN SACs show excellent catalytic performance for the degradation of common antibiotics. Combined with X-ray absorption fine structure and theory calculation, it is confirmed that superficially anchored CoO3 sites of the Co2N2O2-CoO3 unit are the catalytic active center for peroxymonosulfate (PMS) activation. The electrochemical test and in situ electron paramagnetic resonance results demonstrate radical (SO4•- and •OH) and nonradical (electron transfer process and 1O2) paths contributing to the superior catalytic performance. In addition, the catalyst exhibits high reaction efficiency and structural stability considering water quality parameters. Finally, a continuous and efficient device was operated on a laboratory scale, which exhibited satisfactory efficiency in continuously removing electron-rich antibiotics such as tetracycline. This work reveals the atomic-level modulation of cobalt atomic sites on hollow tubular carbon nitride and their structure-activity relationship with persulfate activation.

The Dual Role of Natural Organic Matter in the Degradation of Organic Pollutants by Persulfate-Based Advanced Oxidation Processes: A Mini-Review

Persulfate-based advanced oxidation processes (PS-AOPs) are widely used to degrade significant amounts of organic pollutants (OPs) in water and soil matrices. The effectiveness of these processes is influenced by the presence of natural organic matter (NOM), which is ubiquitous in the environment. However, the mechanisms by which NOM affects the degradation of OPs in PS-AOPs remain poorly documented. This review systematically summarizes the dual effects of NOM in PS-AOPs, including inhibitory and promotional effects. It encompasses the entire process, detailing the interaction between PS and its activators, the fate of reactive oxygen species (ROS), and the transformation of OPs within PS-AOPs. Specifically, the inhibiting mechanisms include the prevention of PS activation, suppression of ROS fate, and conversion of intermediates to their parent compounds. In contrast, the promoting effects involve the enhancement of catalytic effectiveness, contributions to ROS generation, and improved interactions between NOM and OPs. Finally, further studies are required to elucidate the reaction mechanisms of NOM in PS-AOPs and explore the practical applications of PS-AOPs using actual NOM rather than model compounds.

In-depth analysis of the roles and mechanisms of sulfate radical and hydroxyl radical in the degradation of metal-cyanide complexes

Persulfate-based advanced oxidation processes (PS-based AOPs), characterized by the coexistence of SO₄•⁻ and HO•, have been proven effective in treating a series of cyanide-bearing pollutants. However, the mechanisms of these reactive species in the degradation of cyanides, especially metal-cyanide complexes, remain unclear or contradictory. The degradation behavior of representative cyanides (including potassium cyanide and potassium ferricyanide) at different pH conditions (2, 7 and 12) in thermally activated persulfate system (T = 60 °C) was explored, and the roles of SO₄•⁻ and HO• in cyanide degradation were explored by leveraging the distinct characteristics of reactive species under different pH conditions. The study found that both HO• and SO₄•⁻ can react with free cyanide (CN⁻ and HCN). However, the reaction barrier between CN⁻ and HO• is lower than that between HCN and SO₄•⁻, resulting in a higher removal rate of free cyanide under alkaline conditions compared to acidic and neutral conditions. For complexed cyanide, the complex bonds in ferricyanide were completely broken within 24 h by thermally activated persulfate at pH 2, releasing free cyanide, indicating the effectiveness of SO₄•⁻ in breaking the Fe-C bonds in ferricyanide. In contrast, ferricyanide was barely decomposed at pH 12, implying the inefficacy of HO• in breaking the Fe-C bonds. This study also innovatively found that SO₄•⁻ breaks the Fe-C bonds by oxidizing Fe(Ⅲ) in ferricyanide to Fe(Ⅳ) or Fe(Ⅴ), releasing CN⁻, which is then converted to CNO⁻ by SO₄•⁻ and HO•. CNO⁻ is further mineralized to NO₃⁻, NH₄⁺, and N₂ through hydrolysis or oxidation reactions. This research clarifies, for the first time, the activity of SO₄•⁻ and HO• toward cyanide degradation in PS-based AOPs.

MOF derived porous Fe-Cu@carbon catalyst for the degradation of bisphenol A through a persulfate-based advanced oxidation process

A calcination strategy based on the use of mixed MOF HKUST-1/MIL-100 as precursor was used for the obtention of a porous carbon composite (C-HKUST-1/MIL-100) containing iron-copper bimetallic particles within it. The prepared carbon was characterized by XRD, SEM, EDS spectroscopy and N2 adsorption-desorption, confirming the obtention of a micro-mesoporous carbon with Fe-Cu particles homogenously distributed within the structure. For comparison, Cu and Fe-carbons (C-HKUST-1 and C-MIL-100, respectively) were also prepared from the corresponding HKUST-1 and MIL-100 MOFs, respectively. The catalytic performance of the developed carbons as heterogeneous catalysts for persulfate-based advanced oxidation degradation of bisphenol A was evaluated. The Fe-Cu@carbon showed the best catalytic performance, leading to a total BPA degradation after just 10 min of reaction, which was closely related to the synergistic effect of iron and copper. The effect of some key parameters including initial pH value, PS concentration and catalyst dosage was investigated using the Fe-Cu@carbon. In addition, the developed carbon showed good reusability, with no apparent loss in BPA degradation, after five cycles and the ability to treat real water samples, with the advantage that the recovery process after degradation is facilitated thanks to its magnetic properties.

Critical trigger of self-assembled bimetallic Fe/Mn-MOF with SnS2 heterojunctions by persulfate activation for efficient tetracyclines photodegradation

Developing advanced strategies, including exposing active site centers, regulating coordination environments, controlling crystallographic facets, optimizing electronic structures and constructing defects for enhancing photocatalytic performance is of great significance to improving the ecosystem. In this study, a novel self-assembled bimetallic Fe/Mn-MOF with SnS2 Z-scheme heterojunction photocatalyst was designed using a facile multistep solvothermal method. Benefiting from the interfacial heterojunction synergistic effect, the photocatalysts exhibited an outstanding catalytic performance. Nearly 91.4% efficiency of tetracyclines was degraded within 80 min through the assistance of a persulfate-based advanced oxidation process. DFT calculations utilizing the Fukui index identified the sites vulnerable to attack by the active species. As demonstrated by the trapping experiments and electron spin resonance (ESR), the involved oxygen-active species (•O2− and 1O2) facilitated the rapid degradation of tetracycline. The degradation pathways were further guided in the elucidation of the rationale mechanism and the toxicity of derived intermediates was revealed. This work opens a new strategy for the rational design of bimetallic photocatalysts, emphasizing interface-modulated heterojunctions for efficient solar energy conversion.

Excellent bisphenol A removal performance triggered by electron-transfer regime on cobalt phosphide embedded in nitrogen, sulfur-doped carbon/MXene

The non-radical pathway dominated by the electron transfer process (ETP) has gained considerable attention for the removal of organic contaminants in persulfate-based advanced oxidation processes. Rationally designing new catalysts with optimized composition and structural merits and further elucidating the enhanced removal mechanism are of great importance. In this work, we successfully synthesized a nitrogen-sulfur co-doped carbon encapsulated cobalt phosphide (Co2P) on both sides of MXene nanosheets (MZPC) to degrade bisphenol A (BPA) from organic wastewater. The results indicated that BPA was degraded by 98.2 % in a mere 5 min using 0.1 g L-1 of peroxymonosulfate (PMS) and 0.05 g L-1 of the optimized catalyst (MZPC-9), exhibiting an excellent pseudo-first-order kinetics rate constant (k = 1.485 min−1). Uniformly dispersed Co2P nanoparticles (approximately 9.4 nm, calculated using the Scherrer equation) on both sides of MXene exhibited enhanced binding affinity with PMS, forming the MZPC-9-PMS* metastable complexes with potent oxidative capability. The resultant MZPC-9-PMS* complexes induced the polymerization reaction of BPA and achieved 81 % total organic carbon (TOC) removal. This study offers a novel perspective on the design of metal active centers to enhance the ETP-dominated non-radical pathway for pollutant degradation.

Hollow Nanoreactors Unlock New Possibilities for Persulfate-Based Advanced Oxidation Processes.

As a novel type of catalytic material, hollow nanoreactors are expected to bring new development opportunities in the field of persulfate-based advanced oxidation processes due to their peculiar void-confinement, spatial compartmentation, and size-sieving effects. For such materials, however, further clarification on basic concepts and construction strategies, as well as a discussion of the inherent correlation between structure and catalytic activity are still required. In this context, this review aims to provide a state-of-the-art overview of hollow nanoreactors for activating persulfate. Initially, hollow nanoreactors are classified according to the constituent components of the shell structure and their dimensionality. Subsequently, the different construction strategies of hollow nanoreactors are described in detail, while common synthesis methods for these construction strategies are outlined. Furthermore, the most representative advantages of hollow nanoreactors are summarized, and their intrinsic connections to the nanoreactor structure are elucidated. Finally, the challenges and future prospects of hollow nanoreactors are presented.

Progress of persulfate-based advanced oxidation process (PS-AOPs) coupled with ultrafiltration membrane to alleviate membrane fouling: A review

Membrane fouling significantly hampers the extensive deployment of ultrafiltration membranes in treating drinking water. To mitigate fouling and improve filtration effectiveness, advanced oxidation processes (AOPs) have been considered as a potent approach, particularly the activation of AOPs by persulfate (PS-AOPs). Establishing a membrane system based on PS-AOPs is a promising approach to addressing membrane fouling. This article reviews the homogeneous and heterogeneous activation methods of PS. Recent research on the degradation of sulfamethoxazole by various activation methods are summarized, their mechanisms are discussed, and their advantages and disadvantages are compared. The integration of PS-AOPs with UF membranes to control fouling is highlighted, with evidence showing a significant reduction in membrane fouling. The article emphasizes the improvements and limitations of the PS-AOPs coupled with membrane system, especially in heterogeneous systems. Heterogeneous catalysts are doped into membrane materials to form catalytic membranes that can not only participate in membrane filtration but also undergo advanced oxidation upon PS introduction. Finally, the article looks ahead to future research paths and challenges for the PS-AOPs coupled UF membrane system. Based on metal-carbon catalytic membranes, the exploration of materials suitable for activating persulfate is discussed to promote further development of the technology.

Biochar-based persulfate activation: Rate constant prediction, key variables identification, and system optimization

Biochar has emerged as a promising sustainable catalyst for persulfate-based advanced oxidation processes (PS-AOPs), offering synergy between radical and non-radical pathways for superior mineralization. To streamline the traditionally time-consuming and costly biochar selection process, artificial intelligence was employed for a more efficient approach. In this study, an extreme gradient boosting (XGB) model was used to predict the pseudo-first-order kinetic rate constant (k) of a PS-AOPs. Important features were analyzed, and optimal feature values were obtained using particle swarm optimization (PSO). The dataset comprised 671 data points with 18 features extracted from peer-reviewed publications. To address data sparsity and imbalance, machine learning techniques and stratified data splits were utilized, achieving high model performance (R2 = 0.96, RMSE = 0.035). Feature importance analysis using XGB, permutation feature importance, and SHapley Additive exPlanations highlighted the importance of a higher biochar oxygen-to‑carbon ratio and encouraged metal modification. The presence of oxygen functional groups, particularly carbonyl and graphitized biochar structures, was emphasized in kinetic performance. PSO results recommended optimized biochar preparation parameters and operating conditions to enhance the k value, aligning with existing literature. This study predicts kinetic outcomes under preset conditions and guides practical biochar selection, demonstrating its relevance and potential in real-world applications.

Kinetics and mechanisms of non-radically and radically induced degradation of bisphenol A in a peroxymonosulfate-chloride system

Bisphenol A, a hazardous endocrine disruptor, poses significant environmental and human health threats, demanding efficient removal approaches. Traditional biological methods struggle to treat BPA wastewater with high chloride (Cl−) levels due to the toxicity of high Cl− to microorganisms. While persulfate-based advanced oxidation processes (PS-AOPs) have shown promise in removing BPA from high Cl− wastewater, their widespread application is always limited by the high energy and chemical usage costs. Here we show that peroxymonosulfate (PMS) degrades BPA in situ under high Cl− concentrations. BPA was completely removed in 30 min with 0.3 mM PMS and 60 mM Cl−. Non-radical reactive species, notably free chlorine species, including dissolved Cl2(l), HClO, and ClO− dominate the removal of BPA at temperatures ranging from 15 to 60 °C. Besides, free radicals, including •OH and Cl2•−, contribute minimally to BPA removal at 60 °C. Based on the elementary kinetic models, the production rate constant of Cl2(l) (32.5 M−1 s−1) is much higher than HClO (6.5 × 10−4 M−1 s−1), and its degradation rate with BPA (2 × 107 M−1 s−1) is also much faster than HClO (18 M−1 s−1). Furthermore, the degradation of BPA by Cl2(l) and HClO were enlarged by 10- and 18-fold at 60 °C compared to room temperature, suggesting waste heat utilization can enhance treatment performance. Overall, this research provides valuable insights into the effectiveness of direct PMS introduction for removing organic micropollutants from high Cl− wastewater. It further underscores the critical kinetics and mechanisms within the PMS/Cl⁻ system, presenting a cost-effective and environmentally sustainable alternative for wastewater treatment.

Analysis of the steady-state concentrations of reactive species and their role in contaminant degradation by the iron-biochar/persulfate advanced oxidation process: Comparison of probe compound and quenching agent methods

Reactive species, including hydroxyl radicals (OH), sulfate radicals (SO4−), singlet oxygen (1O2), superoxide radicals (O2−), and Fe(IV), are generated by the iron-biochar activated persulfate (Fe-BC/PS) process. These reactive species can be leveraged for treatment of micropollutants, such as the sulfamethoxazole antibiotic. In this study, the steady-state concentrations and contributions of OH, SO4−, 1O2, O2−, and Fe(IV) to sulfamethoxazole degradation were calculated for different operating conditions in the iron-biochar/persulfate (Fe-BC/PS advanced oxidation process. Electron paramagnetic resonance was employed to confirm the production of each reactive species. The nitrobenzene, benzoic acid, furfuryl alcohol, p-chlorobenzoic acid or p-benzoquinone, and phenyl methyl sulfoxide probe compounds were added to experimental solutions in isolation, as mixtures, and at different concentrations to calculate the steady-state concentrations of OH, SO4−, 1O2, O2−, and Fe(IV) and determine their contributions to sulfamethoxazole degradation at variable pH conditions. The results not only informed the primary mechanisms of sulfamethoxazole degradation by the Fe-BC/PS system, but also highlighted best practices for the use of probe compounds and quenching agents in persulfate-based advanced oxidation processes. In particular, the initial concentration of the probe compounds should be as low as possible to avoid impacts on target contaminant degradation and misinterpretation of the role of each reactive species. Furthermore, quenching-based approaches to determination of the key reactive species were less consistent than evaluation by probe compounds. The overall outcomes of this work inform sulfamethoxazole treatment by the Fe-BC/PS system and emphasize the need for internal validation of kinetics results using a multi-pronged approach.

Were Persulfate-Based Advanced Oxidation Processes Really Understood? Basic Concepts, Cognitive Biases, and Experimental Details.

Persulfate (PS)-based advanced oxidation processes (AOPs) for pollutant removal have attracted extensive interest, but some controversies about the identification of reactive species were usually observed. This critical review aims to comprehensively introduce basic concepts and rectify cognitive biases and appeals to pay more attention to experimental details in PS-AOPs, so as to accurately explore reaction mechanisms. The review scientifically summarizes the character, generation, and identification of different reactive species. It then highlights the complexities about the analysis of electron paramagnetic resonance, the uncertainties about the use of probes and scavengers, and the necessities about the determination of scavenger concentration. The importance of the choice of buffer solution, operating mode, terminator, and filter membrane is also emphasized. Finally, we discuss current challenges and future perspectives to alleviate the misinterpretations toward reactive species and reaction mechanisms in PS-AOPs.

The insights into facet-dependent catalytic performance of Cu2O in peroxymonosulfate activation for effective degradation of antibiotics

It was of great significance to improve the performance of catalysts in peroxymonosulfate (PMS) activation for water pollution control. Herein, Cu2O-based catalysts with different exposed facets were synthesized by a feasible method, and later employed for activating PMS to conduct the degradation tests of tetracycline (TC). With the increase of exposed (100) facet, the specific surface area of Cu2O was improved and the interface charge transfer resistance was reduced. More interestingly, benefiting from the exposure of (100) facet, the electron-donating ability of Cu2O was boosted, and the adsorption energy of PMS over Cu2O was also reduced, thereby creating favorable conditions for PMS activation. As guessed, Cu2O-1 with (100) facet can quickly activate PMS to achieve the effective degradation of TC, and the highest removal efficiency of TC over Cu2O-1 can be up to 97.56 % within 15 min. Furthermore, Cu2O-1 with good anti-interference showed satisfactory reusability, and the degradation intermediates of TC were the low toxic or nontoxic. In the Cu2O-1/PMS system, various reactive oxygen species were detected, including SO4•–, OH•, O2•– and 1O2, and wherein the contribution of 1O2 to TC degradation was the greatest. In short, current work shared some valuable insights into persulfate-based advanced oxidation processes.

The Surface Confinement of FeO Assists in the Generation of Singlet Oxygen and High-Valent Metal-Oxo Species for Enhanced Fenton-Like Catalysis.

Transition metal compounds (TMCs) have long been potential candidate catalysts in persulfate-based advanced oxidation process (PS-AOPs) due to their Fenton-like catalyze ability for radical generation. However, the mechanism involved in TMCs-catalyzed nonradical PS-AOPs remains obscure. Herein, the growth of FeO on the Fe3O4/carbon precursor is regulated by restricted pyrolysis of MIL-88A template to activate peroxymonosulfate (PMS) for tetracycline (TC) removal. The higher FeO incorporation conferred a 2.6 times higher degradation performance than that catalyzed by Fe3O4 and also a higher interference resistance to anions or natural organic matter. Unexpectedly, the quenching experiment, probe method, and electron paramagnetic resonance quantitatively revealed that the FeO reassigned high nonradical species (1O2 and FeIV═O) generation to replace original radical system created by Fe3O4. Density functional theory calculation interpreted that PMS molecular on strongly-adsorbed (200) and (220) facets of FeO enjoyed unique polarized electronic reception for surface confinement effect, thus the retained peroxide bond energetically supported the production of 1O2 and FeIV═O. This work promotes the mechanism understanding of TMCs-induced surface-catalyzed persulfate activation and enables them better perform catalytic properties in wastewater treatment.

Activation of peroxymonosulfate and peroxydisulfate by nitrogen-doped carbon nanotubes for effective degradation of neonicotinoid insecticides

Nitrogen-doped carbon nanotubes (N-CNTs) have been considered as an excellent metal-free activator for persulfate-based advanced oxidation processes. However, the critical role of N-doping in the activation of peroxymonosulfate (PMS) and peroxydisulfate (PDS) remains a significant difference even opposed in scientific understanding. Herein, the CNTs and N-CNTs were used to active PMS and PDS for degradation of neonicotinoid insecticides (NNIs), one of the emerging refractory organic pollutants. The N-CNTs achieve 92.6% of nitenpyram (Nit) degradation within only 10 min under PMS system, much higher than that of CNTs/PMS system (∼10%). Moreover, the N-CNTs can active PMS to conduct degradation through a combined 1O2 and electron transfer process with k of 4.94 × 10−2 L·mg−1·min−1, which was quite different from N-CNTs/PDS system (single electron transfer process, k = 1.84 × 10−3 L·mg−1·min−1). A positive correlation between degradation rates of five NNIs and their electron-donating ability is established, further verifying the importance of electron transfer in NNIs degradation. This study proves the superiority of N-CNTs/PMS over N-CNTs/PDS in Nit degradation and the underlying mechanisms, and reveals the importance of electron-donating ability of NNIs in their degradation by N-CNTs/PMS. These findings are of great significance for their removal from the environment.

Mechanical insights into desulfurization by peroxymonosulfate oxidation via a non-reactive oxygen species pathway

Air pollution by sulfur dioxide (SO2) remains a pressing concern for both the environment and human health. Desulfurization enhanced by persulfate based advanced oxidation processes (PS-AOPs) has been proven to be a feasible method. However, the inherent contradiction between the rapid diffusion mass transfer of SO2 in the “gas-liquid-gas” phase and the limited lifespan of reactive oxygen species (ROS) can not be ignored. Excessive investment in PS is required to sustainably generate ROS to achieve continuous desulfurization performance, which may lead to excessive PS consumption. To address this issue, whether PS can achieve the oxidation absorption of SO2 via a non-reactive oxygen species pathway was investigated. Experimental and computational results demonstrated that peroxymonosulfate (PMS) instead of peroxydisulfate (PDS) had a great SO2 removal performance, the utilization of PS could be effectively achieved by maintaining a 1:1 molar ratio of PMS and removed SO2. The presence of HOO bonds in the PMS introduced a partial positive charge to the oxygen atom, making the PMS polar and more susceptible to be attacked by the nucleophile HSO3-. So SO2 underwent a series of processes including dissolution, dissociation, one-oxygen atom transfer, and ionization before ultimately being converted into SO42- ions, effectively achieving its removal from flue gas. This study may presents a novel approach for achieving high-efficiency flue gas desulfurization.

Green mechanochemical activation of solid persulfate to remove PAHs in soil: Performance and mechanism

Due to the high biotoxicity and persistence of polycyclic aromatic hydrocarbons (PAHs), the remediation of PAHs-contaminated soil becomes an intractable problem. Persulfate-based advanced oxidation processes are widely used to degrade PAHs in aquatic environment. However, they are not convenient for used in soil due to the heterogeneity and complexity of soil matrix. In this study, a green and convenient ball milling process is introduced to activate persulfate for the remediation of PAHs-contaminated soil. About 82.5% PAHs were removed with 10% wt. Na2S2O8 (PS) addition and ball-milling for 2 h under 500 r/min. The degradation of PAHs is attributed to the attack of radicals (SO4·- and·OH) generated from the activation of PS by mechanochemistry. Moreover, stable Si-O bonds were disrupted during ball-milling process, and formed free electron on the surface of soil particles. This facilitates the electron transfer from oxidants to contaminants. The particle size, surface element composition, functional group, and thermogravimetric analysis confirmed the slight disturbance of ball-milling-assisted PS process on the physical and chemical properties of soil. Therefore, ball-milling assisted PS approach would be a promising technology for the remediation of PAHs-contaminated soil.

Research progress of persulfate activation technology.

Persulfate-based advanced oxidation processes (PS-AOPs) have been widely investigated by academia and industry due to their high efficiency and selectivity for the removal of trace organic pollutants from complex water substrates. PS-AOPs have been extensively studied for the degradation of pesticides, drugs, halogen compounds, dyes, and other pollutants. Utilizing bibliometric statistics, this review presents a comprehensive overview of persulfate-based advanced oxidation technology research over the past decade. The number of published articles about persulfate activation has steadily increased during this time, reflecting extensive international collaboration. Furthermore, this review introduces the most widely employed strategies for persulfate activation reported in the past 10years, including carbon material activation, photocatalysis, transition metal activation, electrochemical activation, ultrasonic activation, thermal activation, and alkali activation. Next, the potential activation mechanisms and influencing factors, such as persulfate dosage during activation, are discussed. Finally, the application of PS-AOPs in wastewater treatment and in situ groundwater treatment is examined. This review summarizes the previously reported experiences of persulfate-based advanced oxidation technology and presents the current application status of PS-AOPs in organic pollution removal, with the aim of avoiding misunderstandings and providing a solid foundation for future research on the removal of organic pollutants.

Recent advances on the role of high-valent metals formed during persulfate activation

Over the past years, persulfate-based advanced oxidation processes have been widely employed in scientific research and practical application because of their outstanding oxidizing capability for decontamination and sterilization. In contrast to SO4•− and •OH radicals that are commonly considered to be the primary reactive oxidants, high-valent metals, such as Fe(IV), Co(IV), Cu(III), and Mn(V), formed during persulfate activation have only been observed in recent years. The advantages of high-valent metals over radicals lie in the better tolerance of background ions and the selective reaction towards compounds containing electron-rich groups. In this review, current research progress on high-valent metals generated during persulfate activation is outlined, and the formation mechanism, oxidation performance, and practical application are discussed. Specifically, the formation of high-valent metals has been observed via 18O-labeled water combined with chemical probes and in situ spectroscopy; compared to radicals, the formation of these metals was more thermodynamically favorable. Unlike •OH and SO4•−, which exhibit strong and nonselective reactivity, high-valent metals possess moderate oxidation power and selectively react with compounds containing electron-rich groups; these reactions are affected by several parameters, such as pH, temperature, activator/persulfate dosage, and ligand. The applications of high-valent metal-mediated oxidation processes and challenges encountered are discussed. Overall, potential applications of high-valent metal-mediated oxidation based on persulfate could be extended for practical wastewater treatment.

Underestimated role of hydroxyl radicals for bromate formation in persulfate-based advanced oxidation processes

In persulfate-based advanced oxidation processes (PS-AOPs), sulfate radicals (SO4•-) have been recognized to play more important roles in inducing bromate (BrO3−) formation rather than hydroxyl radicals (HO•) because of the stronger oxidation capacity of the former. However, this study reported an opposite result that HO• indeed dominated the formation of bromate instead of SO4•-. Quenching experiments were coupled with electron paramagnetic resonance (EPR) detection and chemical probe identification to elucidate the contributions of each radical species. The comparison of different thermal activated persulfates (PDS and PMS) demonstrated that the significant higher bromate formation in HEAT/PMS ([BrO3−]/[Br−]0 = 0.8), as compared to HEAT/PDS ([BrO3−]/[Br−]0 = 0.2), was attributable to the higher concentration of HO• radicals in HEAT/PMS. Similarly, the bromate formation in UV/PDS ([BrO3−]/[Br−]0 = 1.0), with a high concentration of HO•, further underscored the dominant role of HO•. As a result, we quantified that HO• and SO4•- radicals accounted 66.7% and 33.3% for bromate formation. This controversial result can be reconciled by considering the critical intermediate, hypobromic acid/hypobromate (HOBr/BrO−), involved in the transformation of Br− to BrO3−. HO• radicals have the chemical preference to induce the formation of HOBr/BrO− intermediates (contributing ∼ 60%) relative to SO4•- radicals (contributing ∼ 40%). This study highlighted the dominant role of HO• in the formation of bromate rather than SO4•- in PS-AOPs and potentially offered novel insights for reducing disinfection byproduct formation by controlling the radical species in AOPs.