Persulfate-based Advanced Oxidation Processes Research Articles

Potential of metallurgical iron-containing solid waste-based catalysts as activator of persulfate for organic pollutants degradation.

The production of solid wastes in the metallurgical industry has significant implications for land resources and environmental pollution. To address this issue, it is crucial to explore the potential of recycling these solid wastes to reduce land occupation while protecting the environment and promoting resource utilization. Steel slag, red mud, copper slag and steel picking waste liquor are examples of solid wastes generated during the metallurgical process that possess high iron content and Fe species, making them excellent catalysts for persulfate-based advanced oxidation processes (PS-AOPs). This review elucidates the catalytic mechanisms and pathways of Fe2+ and Fe0 in the activation PS. Additionally, it underscores the potential of metallurgical iron-containing solid waste (MISW) as a catalyst for PS activation, offering a viable strategy for its high-value utilization. Lastly, the article provides an outlook towards future challenges and prospects for MISW in PS activation for the degradation of organic pollutants.

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 10min 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 × 10-2L·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.

N-doped carbon polyhedron-modified Co@N-doped carbon nanotube with enhanced [formula omitted] production for selective removal of organic pollutants

Persulfate-based advanced oxidation process dominated by singlet oxygen (1O2) shows potential for targeted degradation of organic pollutants but the regulation of 1O2 generation is still challenging. In this study, N-doped carbon polyhedron-modified Co@N-doped carbon nanotube (NCP/Co@NCNT) were successfully fabricated. The as-obtained NCP/Co@NCNT demonstrated a much enhanced 1O2 production in activating peroxymonosulfate (PMS) because of the nanoconfinement effect of metallic Co nanoparticles encapsulated in NCNT, which was further confirmed by density functional theory calculations. The NCP/Co@NCNT/PMS system has excellent catalytic performance and is capable of removing 97 % of carbamazepine (CBZ) in 55 min (Catalyst: 0.1 g/L, CBZ: 20 mg/L, PMS: 0.5 g/L). Quantitative structure–activity relationship (QSAR) analysis uncovered a positive correlation between the oxidation kinetics of organic pollutants and their EHOMO. Specifically, pollutants with higher EHOMO are more easily oxidized in the 1O2-dominated NCP/Co@NCNT/PMS system. Furthermore, the generated intermediates exhibited low toxicity in the system with 1O2 as the primary active species. This study offers an effective approach to prepare catalysts for the selective elimination of organic micropollutants in complex water environments.

Magnetic MoS2/Fe3O4 composite as an effective activator of persulfate for the degradation of tetracycline: performance, activation mechanisms and degradation pathways

ABSTRACT The activated persulfate (PS) process could produce sulfate radical (SO4·-) and rapidly degrade organic pollutants. The application of Fe3O4 as a promising PS activator was limited due to the rapid conversion of Fe2+ to Fe3+ on its surface. Mo4+ on MoS2 surface could be used as a reducing site to convert Fe3+ to Fe2+, but the separation and recovery of MoS2 was complex. In this study, MoS2/Fe3O4 was prepared to accelerate the Fe3+/Fe2+ cycle on Fe3O4 surface and achieved efficient separation of MoS2. The results showed that MoS2/Fe3O4 was more effective for PS activation compared to Fe3O4 or MoS2, with a removal efficiency of 91.8% for 20 mg·L−1 tetracycline (TC) solution under the optimal conditions. Fe2+ and Mo4+ on MoS2/Fe3O4 surface acted as active sites for PS activation with the generation of SO4•−, •OH, •O2−, and 1O2. Mo4+ acted as an electron donor to promote the Fe3+/Fe2+ cycling and thus improved the PS activation capability of MoS2/Fe3O4. The degradation pathways of TC were inferred as hydroxylation, ketylation of dimethylamino group and C-N bond breaking. This study provided a promising activated persulfate-based advanced oxidation process for the efficient degradation of TC by employing MoS2/Fe3O4 as an effective activator.

Persulfate-Based Advanced Oxidation Process for Chlorpyrifos Degradation: Mechanism, Kinetics, and Toxicity Assessment.

Persulfate-based advanced oxidation process has been proven to be a promising method for the toxic pesticide chlorpyrifos (CPY) degradation in wastewater treatment. However, due to the limitation for the short-lived intermediates detection, a comprehensive understanding for the degradation pathway remains unclear. To address this issue, density functional theory was used to analyze the degradation mechanism of CPY at the M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G(d,p) level, and computational toxicology methods were employed to explore the toxicity of CPY and its degradation products. Results show that hydroxyl radicals (·OH) and sulfate radicals (SO4•-) initiate the degradation reactions by adding to the P=S bond and abstracting the H atom on the ethyl group, rather than undergoing α-elimination of the pyridine ring in the persulfate oxidation process. Moreover, the addition products were attracted and degraded by breaking the P-O bond, while the abstraction products were degraded through dealkylation reactions. The transformation products, including 3,5,6-trichloro-2-pyridynol, O,O-diethyl phosphorothioate, chlorpyrifos oxon, and acetaldehyde, obtained through theoretical calculations have been detected in previous experimental studies. The reaction rate constants of CPY with ·OH and SO4•- were 6.32 × 108 and 9.14 × 108 M-1·s-1 at room temperature, respectively, which was consistent with the experimental values of 4.42 × 109 and 4.5 × 109 M-1 s-1. Toxicity evaluation results indicated that the acute and chronic toxicity to aquatic organisms gradually decreased during the degradation process. However, some products still possess toxic or highly toxic levels, which may pose risks to human health. These research findings contribute to understanding the transformation behavior and risk assessment of CPY in practical wastewater treatment.

Sustainable and Rapid Water Purification at the Confined Hydrogel Interface.

Emerging organic contaminants in water matrices have challenged ecosystems and human health safety. Persulfate-based advanced oxidation processes (PS-AOPs) have attracted much attention as they address potential water purification challenges. However, overcoming the mass transfer constraint and the catalyst's inherent site agglomeration in the heterogeneous system remains urgent. Herein, the abundant metal-anchored loading (≈6-8g m-2) of alginate hydrogel membranes coupled with cross-flow mode as an efficient strategy for water purification applications is proposed. The organic flux of the confined hydrogel interfaces sharply enlarges with the reduction of the thickness of the boundary layer via the pressure field. The normalized property of the system displays a remarkable organic (sulfonamides) elimination rate of 4.87 × 104mg min-1 mol-1. Furthermore, due to the fast reaction time (<1min), cross-flow mode only reaches a meager energy cost (≈2.21Wh m-3) under the pressure drive field. It is anticipated that this finding provides insight into the novel design with ultrafast organic removal performance and low techno-economic cost (i.e., energy operation cost, material, and reagent cost) for the field of water purification under various PS-AOPs challenging scenarios.

In Situ Monitoring of the Polymerization Kinetics of Organic Pollutants during Persulfate-Based Advanced Oxidation Processes Using Plasmonic Colorimetry.

Using sulfate radicals to initiate polymer production in persulfate-based advanced oxidation processes (AOPs) is an emerging strategy for organics removal. However, our understanding of this process remains limited due to a dearth of efficient methods for in situ and real time monitoring of polymerization kinetics. This study leverages plasmonic colorimetry to monitor the polymerization kinetics of an array of aromatic pollutants in the presence of sulfate radicals. We observed that the formation of polymer shells on the surfaces of gold nanoparticles (AuNPs) led to an increase and red shift in their localized surface plasmon resonance (LSPR) band as a result of an increased refractive index surrounding the AuNP surfaces. This observation aligns with Mie theory simulations and transmission electron microscopy-electron energy loss spectroscopy characterizations. Our study demonstrated that the polymerization kinetics exhibits a significant reliance on the electrophilicity and quantity of benzene rings, the concentration of aromatic pollutants, and the dosage of oxidants. In addition, we found that changes in LSPR band wavelength fit well into a pseudo-first-order kinetic model, providing a comprehensive and quantitative insight into the polymerization kinetics involving diverse organic compounds. This technique holds the potential for optimizing AOP-based water treatment by facilitating the polymerization of aromatic pollutants.

From nano- to macroarchitectures: designing and constructing MOF-derived porous materials for persulfate-based advanced oxidation processes.

Persulfate-based advanced oxidation processes (PS-AOPs) have gained significant attention as an effective approach for the elimination of emerging organic contaminants (EOCs) in water treatment. Metal-organic frameworks (MOFs) and their derivatives are regarded as promising catalysts for activating peroxydisulfate (PDS) and peroxymonosulfate (PMS) due to their tunable and diverse structure and composition. By the rational nanoarchitectured design of MOF-derived nanomaterials, the excellent performance and customized functions can be achieved. However, the intrinsic fine powder form and agglomeration ability of MOF-derived nanomaterials have limited their practical engineering application. Recently, a great deal of effort has been put into shaping MOFs into macroscopic objects without sacrificing the performance. This review presents recent advances in the design and synthetic strategies of MOF-derived nano- and macroarchitectures for PS-AOPs to degrade EOCs. Firstly, the strategies of preparing MOF-derived diverse nanoarchitectures including hierarchically porous, hollow, yolk-shell, and multi-shell structures are comprehensively summarized. Subsequently, the approaches of manufacturing MOF-based macroarchitectures are introduced in detail. Moreover, the PS-AOP application and mechanisms of MOF-derived nano- and macromaterials as catalysts to eliminate EOCs are discussed. Finally, the prospects and challenges of MOF-derived materials in PS-AOPs are discussed. This work will hopefully guide the design and development of MOF-derived porous materials in SR-AOPs.

Reductive carbon tetrachloride degradation by surfactant derived radicals in persulfate activation system

Despite the wide range of applications for persulfate-based advanced oxidation processes (PS-based AOPs) in groundwater remediation, the elimination of perchlorinated hydrocarbon contaminants such as carbon tetrachloride (CT) remains a challenge. In this research, we discovered that CT degradation in PS/Fe(II) system was greatly promoted with the presence of surfactant Tween-80 (TW-80), whereas it was hardly removed without TW-80 presence. The introduction of citric acid (CA) or nano zero-valent iron (nZVI) could both enhance the efficacy of PS/Fe(II) system. Through scavenging experiments and electron paramagnetic resonance analysis, the generated secondary surfactant radicals (R•CHOH) from TW-80 and superoxide radicals (O2−•) were identified as the driving factors behind CT degradation. CT dechlorination reached 70.6% and 71.8% in PS/Fe(II)/CA and PS/Fe(II)/nZVI systems, respectively, and the potential degradation routes of CT were offered. Additionally, the effect of TW-80 concentration and solution matrixes (solution pH and inorganic ions) on CT degradation was assessed. Furthermore, the removal of mixed chlorinated hydrocarbon contaminants and actual groundwater tests were also performed. Given that surfactants are commonly used in soil and groundwater remediation, this research provides a new prospect and theoretical support for the treatment of perchlorinated contaminants in groundwater with the presence of surfactants.

Role of Interface of Metal-Organic Frameworks and Their Composites in Persulfate-Based Advanced Oxidation Process for Water Purification.

The persulfate activation-based advanced oxidation process (PS-AOP) is an important technology in wastewater purification. Using metal-organic frameworks (MOFs) as heterogeneous catalysts in the PS-AOP showed good application potential. Considering the intrinsic advantages and disadvantages of MOF materials, combining MOFs with other functional materials has also shown excellent PS activation performance and even achieves certain functional expansion. This Review introduces the classification of MOFs and MOF-based composites and the latest progress of their application in PS-AOP systems. The relevant activation/degradation mechanisms are summarized and discussed. Moreover, the importance of catalyst-related interfacial interaction for developing and optimizing advanced oxidation systems is emphasized. Then, the interference behavior of environmental parameters on the interfacial reaction is analyzed. Specifically, the initial solution pH and coexisting inorganic anions may hinder the interfacial reaction process via the consumption of reactive oxygen species, affecting the activation/degradation process. This Review aims to explore and summarize the interfacial mechanism of MOF-based catalysts in the activation of PS. Hopefully, it will inspire researchers to develop new AOP strategies with more application prospects.

Analysis of scientific and technological trends in the incorporation of activated carbon in advanced oxidation processes-a bibliometric study.

There is high interest in the development of water pollution remediation technologies. Advanced oxidation processes (AOPs) are a promising alternative for the degradation of organic compounds; however, these technologies have been limited mainly by high operating costs and, in some cases, by forming byproducts, which can be more hazardous than the original pollutants. Activated carbon (AC) is a porous material that can be combined with AOP systems in various ways, given its adsorbent and catalytic characteristics. In addition, AC is a flexible, adaptable, and low-cost material. This article presents a bibliometric analysis of AOPs incorporating CA in scientific research and patents; the Scopus database was used to obtain patents and Orbit Express for patents. The most investigated AOPs incorporating AC are photocatalysis processes, Fenton processes, persulfate-based AOP, electrochemical processes, and ozonation. However, it is the persulfate-based AOP that has seen the greatest growth in scientific publications in recent years; this great interest can be related to the synergy that the process has with AC, allowing the degradation of contaminants via radical and non-radical. According to the maturity analysis of scientific publications, photocatalysis, Fenton, electrochemistry, ozonation, and persulfate technologies are in a growth stage and will reach maturity in 2034, 2042, 2040, 2034, and 2035, respectively; these technologies coupled with AC are expected to generate a greater number of patents when they reach maturity.

Efficient activation of peroxydisulfate by modified red mud biochar derived from waste corn straw for levofloxacin degradation: Efficiencies and mechanisms

As using iron-based materials and biomass to prepare effective catalyst has emerged as a hit trend in persulfate-based advanced oxidation processes (PS-AOPs), the problems associated with excessive chemical consumption, costly expenses, and complex synthetic processes have become more urgent to be addressed. Therefore, by using red mud (RM) and corn straw (CS), a modified red mud biochar catalyst (MRBC) was synthesized through acid pretreatment and pyrolysis (700 °C). MRBC presented excellently in peroxydisulfate (PDS) activation to degrade levofloxacin (LFX). Under the experimental setup involving 8 mM PDS, 10 mg L−1 LFX, and 1.6 g L−1 MRBC, 88.59% of LFX was effectively eliminated within 30 min with an exceedingly low Fe leaching rate of 0.049 mg L−1. Furthermore, even after four cycles of reuse, it was able to sustain a remarkable 61.63% efficiency in LFX degradation. The characterization of catalysts demonstrated the synergistic effect of RM and biomass could be responsible for the excellent catalytic properties of MRBC. The results of quenching experiment and the presence of DMPOX in EPR demonstrated radical pathway mainly contributed to the LFX degradation in MRBC/PDS system. Overall, PDS was activated by the active sites of MRBC such as Fe (II) and persistent free radicals (PFRs) to generate a large amount of SO4•− and •OH to remove LFX. This work investigated the synergy of RM and biomass in catalyst preparation, deepened the insights into the application of RM catalysts in PS-AOPs to degrade antibiotic, and contributed greatly to the recovery of waste resources.

Synergy of radical and nonradical degradations triggered by self-floating MnO2/cotton hydrogels with photothermal effect and oxygen vacancy

Persulfate-based advanced oxidation process is a promising technology for the water purification. While the synergy of radical and nonradical degradations are still unfeasible during persulfate activation, which process consumes a large amount of external energy. The self-floating manganese dioxide (MnO2)/cotton hydrogels (MCH) was developed, which achieves solar energy capture and wastewater treatment. In this study, a meticulously designed MCH enables simultaneous interface heating and persulfate activation. The MCH exhibited an excellent photothermal conversion capability with an evaporation rate of 2.89 kg/(m2·h) under 1 sun. The MCH coupled with peroxydisulfate (PDS) achieved a tetracycline (TC) degradation efficiency of 74.53 % under a visible light irradiation in 120 min. Furthermore, the result of TC evaporation experiment showed that 99.43 % of TC can be removed from the evaporated water. Interestingly, it was found that the singlet oxygen (1O2) increased with the concentration of Vo in the MCH during PDS activation process. In contrast to the conventional view, the thermal effect increases the concentration of Vo thus promoting the conversion of superoxide radicals (O2−) to 1O2 in the presence of Mn4+. Additionally, the polyvinyl alcohol/polyvinylpyrrolidone (PVA/PVP) hydrogel with porous structure that provided the oxygen for MnO2, promoting the production of reactive oxygen species. This study provides a new model for simultaneous evaporation and degradation, which deepens the understanding of synergy of radical and nonradical degradations.

Bimetallic Bi/Cu0-catalyzed persulfate-based advanced oxidation processes towards clofibric acid degradation in wastewater

Clofibric acid (CFA), an important blood-lipid regulatory drug is an emerging organic pollutant and widely reported in water resources. A novel bimetallic, bismuth/zero valent cupper (Bi/Cu0) catalyst was prepared which showed better physiological, structural, and catalytic properties than Cu0. The Bi/Cu0 effectively catalyzed persulfate (S2O82−) and caused 85% degradation of CFA. The Bi coupling improved reusability and stability of Cu0. The use of alcoholic and anionic radical scavengers and analyzing change in [S2O82−]0 proved that Bi/Cu0/S2O82− yield hydroxyl radicals (●OH) and sulfate radicals (SO4●–). The ●OH and SO4●– showed faster reaction with CFA, i.e., 4.65 × 109 and 3.82 × 109 M−1 s−1 and degraded CFA into four degradation products. Under optimal conditions of [Bi/Cu0]0 = 1.0 g/L and [S2O82−]0 = 40 mg/L, 99.5% degradation of the 10 mg/L of CFA was achieved at 65 min. Temperature showed promising effects on the removal of CFA by Bi/Cu0/S2O82− and caused 98% removal at 323 K than 75% at 298 K at 32 min. The temperature effects were used to calculate activation energy, enthalpy, and rate constant of CFA degradation. The Bi/Cu0/S2O82− showed effective removal of CFA in real water samples also. The ecotoxicity study confirmed non-toxic product formation which suggests high capability of the proposed technology in the treatment of CFA.

Comparison of TiO2 and ZnO for Heterogeneous Photocatalytic Activation of the Peroxydisulfate Ion in Trimethoprim Degradation.

The persulfate-based advanced oxidation process is a promising method for degrading organic pollutants. Herein, TiO2 and ZnO photocatalysts were combined with the peroxydisulfate ion (PDS) to enhance the efficiency. ZnO was significantly more efficient in PDS conversion and SO4•- generation than TiO2. For ZnO, the PDS increased the transformation rate of the trimethoprim antibiotic from 1.58 × 10-7 M s-1 to 6.83 × 10-7 M s-1. However, in the case of TiO2, the moderated positive effect was manifested mainly in O2-free suspensions. The impact of dissolved O2 and trimethoprim on PDS transformation was also studied. The results reflected that the interaction of O2, PDS, and TRIM with the surface of the photocatalyst and their competition for photogenerated charges must be considered. The effect of radical scavengers confirmed that in addition to SO4•-, •OH plays an essential role even in O2-free suspensions, and the contribution of SO4•- to the transformation is much more significant for ZnO than for TiO2. The negative impact of biologically treated domestic wastewater as a matrix was manifested, most probably because of the radical scavenging capacity of Cl- and HCO3-. Nevertheless, in the case of ZnO, the positive effect of PDS successfully overcompensates that, due to the efficient SO4•- generation. Reusability tests were performed in Milli-Q water and biologically treated domestic wastewater, and only a slight decrease in the reactivity of ZnO photocatalysts was observed.