Heterogeneous Oxidation Processes Research Articles

Influence of S(IV) reduction on the reaction mechanisms and the generation of reactive oxygen species in B-Cu@Fe/PPS system

Heterogeneous sulfite-based advanced oxidation process is extremely promising for the removal of various industrial pollutants owing to its generation of multiple reactive oxygen species (ROS), while the unclear mechanism of S(IV) conversion and ROS generation hinder its practical applications. Here, the iron-copper bimetallic was synthesized for potassium pyrosulfate catalysis, which was designed for insight into the mechanism of micropollutant degradation driven by sulfur species conversion. Experimental and theoretical calculations have shown that the reaction process and corresponding mechanisms can be significantly distinguished into three different stages. Stage one prepares sufficient Fe(III) for the initiation of the reaction, while stage two generating ROS and reduces S(IV). In the stage three, the low-valent sulfur produced from S(IV) combines with iron-copper materials to form highly active sulfur sites, which react with O2 to generate a large number of hydroxyl radicals (•OH). Furthermore, a variety of contaminants were used to validate the universality of the system, and their wide distribution in wastewater implies broad application prospects. This research provides in-depth interpretations of the induced mechanism of sulfur species conversion in the sulfite heterogeneous system, provides a solid theoretical foundation for the engineering application of the system.

Heterogeneous oxidation involving different atomic clusters in sintering-free amorphous SiBCN ceramic with MA@PDC-SiBCN structure

Amorphous SiBCN monoliths featuring a structure of three-dimensional PDC-SiBCN network encapsulating MA-SiBCN nanoparticles (MA@PDC-SiBCN), were prepared without the need for sintering densification (>1800°C), enabling preparation of dense ceramics at a much lower temperature (1100°C). The continuous PDC-SiBCN network effectively inhibits oxygen diffusion, reducing the mass loss from B-C-N cluster oxidation and mass gain from silicon-containing clusters by 51.5% and 86.9%, respectively. Besides, the phase-separation coupled heterogeneous oxidation behaviors and kinetics of different atomic clusters in MA@PDC-SiBCN ceramic during non-isothermal oxidation up to 1500°C were investigated. Finally, the evolution of the different atomic clusters within the oxide layer during the heterogeneous oxidation process was analyzed to elucidate the micro-mechanisms behind the enhanced oxidation resistance.

Insight in sulfadiazine degradation by peroxymonosulfate activated by polydopamine-derived nitrogen-doped carbon supported CoFe2O4: Co leaching inhibition and degradation enhancement

Heterogeneous catalyst-mediated sulfate radical-based advanced oxidation processes (SR-AOPs) showed excellent performance during antibiotics degradation. Spinel was a promising catalyst for SR-AOPs, but the secondary contamination due to metal ions leaching needed to be addressed. And the destruction of catalyst structure could lead to the reduction of catalytic activity and the difficulty of recovery. Thus, a novel nitrogen-doped carbon (NC)-supported CoFe2O4 (CoFe2O4@NC) was synthesized as the activator of PMS for sulfadiazine (SDZ) degradation under low Co leaching conditions. The consequences indicated that the CoFe2O4@NC/PMS system exhibited higher PMS decomposition efficiency and reaction stoichiometry efficiency than the bare CoFe2O4/PMS systems (CoFe2O4-180 and CoFe2O4-800), which in turn demonstrated a better SDZ removal performance. Under the condition of CoFe2O4@NC dosage 0.1 g/L, PMS concentration 0.5 mM, solution pH 6.8 and temperature 25°C, SDZ (20 mg/L) was almost completely degraded within 60 min. XPS analysis showed that the NC not only protected and stabilized CoFe2O4, but also provided additional active sites for PMS activation. During SDZ degradation, SO4•−, HO•, •O2− and 1O2 were involved in the reaction, among which SO4• and HO• made the main contribution. Meanwhile, CoFe2O4@NC could be recovered by magnetic separation, and showed great stability (Co leaching 0.852 mg/L) and reusability. In the fifth cycle experiment, 85.02 % SDZ degradation was obtained. Based on the detected intermediates (12 intermediates were identified) and DFT calculations, possible degradation pathways for SDZ in CoFe2O4@NC/PMS were proposed. The condensed dual descriptor indicated that the N7, N11, and C15 atoms on SDZ molecule were the main sites of electrophilic attack, which was consistent with the detected intermediates. The degradation of SDZ involved hydroxylation of NH2, cleavage of S−N and extrusion of SO2. This study explored the improvements made in NC support material to catalytic performance and resistance to dissolution of spinel, providing new insights for subsequent researches.

Flotation separation of ilmenite and titanaugite modified by Fe2+-assisted peroxymonosulfate oxidation: Performance and activation mechanism

Efficient separation of ilmenite and titanaugite has always been recognized challenge in modern mineral processing. The use of a heterogeneous Fenton-like oxidation process composed of peroxymonosulfate (PMS) and Fe2+ is promising to address this issue. Flotation findings indicated that effective recovery of ilmenite could be achieved under weak acidic conditions, and a TiO2 recovery of 81.56 % and a grade of 32.16 % concentrate was collected. A series of characterization analyses confirmed that the PMS-Fe2+-mediated Fenton-like reaction in the ilmenite system generated more •OH and SO4•- radicals, which oxidized Fe2+ to Fe3+ on its surface, thus improving the active sites on ilmenite surface. Moreover, PMS-Fe2+ promoted the positive shift of surface charge on ilmenite, facilitating NaOL adsorption and making the surface more hydrophobic. NaOL primarily interacted with Fe active sites on the ilmenite surface and Mg2+ and Ca2+ active sites on the titanaugite surface in the formation as chemisorption. Thus, PMS-Fe2+ activated ilmenite mainly via augmenting the quantity and reactivity of Fe active sites on the surface. In summary, these findings provide the innovative pathways to implement the advanced oxidation processes in mineral flotation.

Homogeneous versus heterogeneous Mn(II) oxidation in peroxymonosulfate assisting chlorination: Synergistic role for enhanced Mn(II) oxidation in water treatment

Removal of Mn(II) is an essential step for addressing water discoloration in water treatment utilities worldwide. However, conventional chlorination suffers from poor oxidation of Mn(II) due to its low homogeneous oxidation kinetics. This study explored the oxidation capability of a new chemical dosing strategy employing peroxymonosulfate (PMS) to assist the chlorination process (PMS@Cl2) for effective Mn(II) oxidation. The study comprehensively explored both oxidation kinetics and underlying mechanisms associated with homogeneous and heterogeneous oxidation within the PMS@Cl2 system. At an [Mn(II)]0 of 1 mg/L, chlorination demonstrated inability in oxidizing Mn(II), with <10 % oxidation even at an elevated [Cl2] of 150 μM (∼10 mg/L). By contrast, PMS completely oxidized 100 % Mn(II) within a 30-minute reaction at a much lower [PMS] of 60 μM (kobs = 0.07 min−1 and t1/2 = 9 min), demonstrating its superior Mn(II) oxidation kinetics (over one order of magnitude faster than conventional chlorine). PMS@Cl2 exhibited an interesting synergistic benefit when combining a lower dose PMS with a higher routine dose Cl2 (loPMS@hiCl2), e.g. [PMS]:[Cl2] at 15:30 or 30:30 μM. Both conditions achieved 100 % Mn(II) oxidation, with even better values of kobs and t1/2 (0.16–0.17 min−1 and ∼4 min) relative to PMS alone at 60 µM. The synergic benefit of PMS@Cl2 was attributed to distinct functions played by PMS and Cl2 in both homogeneous and heterogeneous oxidation processes. Reactive species identification excluded the possible involvement of SO4•−, OH•, or chlorine radicals in the homogeneous oxidation of the PMS@Cl2 system. Instead, the dominant species was O2•− radical generated during the reaction of Mn(II) and PMS. Furthermore, the heterogeneous oxidation emphasized the important role of combining Cl2 dosing, which demonstrated an increased reactivity and electron transfer with the Mn−O−Mn complex, surpassing PMS. Overall, heterogeneous oxidation accelerated the oxidation kinetics of the PMS@Cl2 system by 1.1–2 orders of magnitude relative to the homogeneous oxidation of Cl2 alone. We here demonstrated that PMS@Cl2 could offer a more efficient mean of soluble Mn(II) mitigation, achieved with a relatively low routine dose of oxidant in a short reaction period. The outcomes of this study would address the existing limitations of traditional chlorine oxidation, minimizing the trade-offs associated with high residual chlorine levels after treatments for soluble manganese-containing water.

Kinetic Study and Catalytic Activity of Cr3+ Catalyst Supported on Calcium Silicate Hydrates for VOC Oxidation.

Volatile organic compounds (VOCs) are pollutants that pose significant health and environmental risks, necessitating effective mitigation strategies. Catalytic oxidation emerges as a viable method for converting VOCs into non-toxic end products. This study focuses on synthesizing a catalyst based on calcium silicate hydrates with chromium ions in the CaO-SiO2-Cr(NO3)3-H2O system under hydrothermal conditions and evaluating its thermal stability and catalytic performance. A catalyst with varying concentrations of chromium ions (10, 25, 50, 100 mg/g Cr3+) was synthesized in unstirred suspensions under saturated steam pressure at a temperature of 220 °C. Isothermal curing durations were 8 h, 16 h, and 48 h. Results of X-ray diffraction and atomic absorption spectroscopy showed that hydrothermal synthesis is effective for incorporating up to 100 mg/g Cr3+ into calcium silicate hydrates. The catalyst with Cr3+ ions (50 mg/g) remained stable up to 550 °C, beyond which chromatite was formed. Catalytic oxidation experiments with propanol and propyl acetate revealed that the Cr3+ catalyst supported on calcium silicate hydrates enhances oxygen exchange during the heterogeneous oxidation process. Kinetic calculations indicated that the synthesized catalyst is active, with an activation energy lower than 65 kJ/mol. This study highlights the potential of Cr3+-intercalated calcium silicate hydrates as efficient catalysts for VOC oxidation.

Enhanced mineralization of bisphenol A by electric arc furnace slag: Fenton-like oxidation

Bisphenol A (BPA) aqueous solution was treated through a heterogeneous Fenton-like oxidation process with electric arc furnace slag (EAFS), a waste product from an Argentinian steel processing plant, as the catalyst. SEM/EDS, XRD, and Mössbauer spectroscopy characterization revealed a significant presence of Fe and minor amounts of Cu and Mn in EAFS, known to play active roles in the Fenton-like reactions. The predominant crystalline form of iron in EAFS was magnesiowüstite, accompanied by minor amounts of hematite, magnetite, maghemite, and metallic iron. Batch Fenton-like oxidation experiments were conducted under acidic conditions (pH 2.8–3), examining the effect of temperature (25, 50, and 70 °C) and catalyst load (0.1, 0.5, and 1 g/L) on BPA degradation and mineralization over 180 min. BPA was completely degraded within the first minutes, while mineralization levels improved from 40% to an outstanding 70% as the temperature increased from 25 to 70 °C. The catalyst gradually lost its activity after five cycles at 25 °C, but raising the temperature up to 70 °C allowed maintaining mineralization levels between 70 and 50% over ten cycles. The oxidation process involved a combined Fenton-like homogeneous/heterogeneous mechanism, and deactivation was linked to a lower leaching of active cations over the cycles, reduction of the Fe(II)/Fe(III) ratio in the iron phases, and blocking of active sites by adsorption of reaction intermediates. EAFS demonstrated an exceptional performance in the Fenton-like oxidation of BPA. The utilization of this type of industrial waste materials represents a promising technological alternative that could benefit both steel processing and water treatment plants.

Stress-Alteration Enhancement of the Reactivity of Aluminum Nanoparticles in the Catalytic Decomposition of exo-Tetrahydrodicyclopentadiene (JP-10).

High-energy-density aluminum nanoparticles (AlNPs) upon thermal annealing followed by superquenching result in elevated stress levels in the metallic core and reduced surface energy at the core-shell interface. Isomer-selective vacuum ultraviolet-based photoionization mass spectrometry coupled to a high-temperature chemical microreactor reveals that these stress-altered AlNPs (SA-AlNPs) exhibit distinctive temperature-dependent reactivities toward catalytic decomposition of the hydrocarbon jet fuel exo-tetrahydrodicyclopentadiene (JP-10, C10H16) compared to untreated AlNPs (UN-AlNPs). SA-AlNPs show a delayed initiation of the decomposition for JP-10 by 200 K relative to the UN-AlNPs; however, the full decomposition is achieved at a 100 K lower temperature. Furthermore, there are fewer oxygenated products that are generated from the alumina surface-induced heterogeneous oxidation process and a larger fraction of closed- and open-shell hydrocarbons. Chemical insight bridging the reactivity order of SA-AlNPs at low and high temperatures, simultaneously, is obtained via a detailed examination of the product branching ratios obtained in this study.

Spatial Confinement of Co Nanoparticles in N-Doped Carbon Nanorods for Wastewater Purification via CaSO3 Activation.

Spatial confinement of organic pollutants and reactive oxygen species (e.g., SO4•- and •OH) with ultrashort lifetime inside the scale of chemical theoretical diffusion could provide a greatly promising strategy to overcome the limitation of mass transfer in the heterogeneous Fenton-like oxidation process. Herein, we first reported spatial confinement of cobalt nanoparticles in N-doped carbon nanorods (Co-NCNRs), by encapsulating Co nanoparticles into N-doped carbon nanorods, in activating CaSO3 for antibiotic degradation. Compared to Na2SO3 and NaHSO3, CaSO3 could slowly and persistently discharge SO32- due to its low solubility, thus avoiding the depletion of the generated SO3•- and •OH under the high concentration of sulfite ions. Fully physical characterizations confirmed that the 3D hydrogel was mostly transformed into the nanorod structure of Co-NCNRs at 550 °C. Co atoms were successfully nanoconfined into N-doped carbon nanorods, which contributes to mass transfer and prevents the agglomeration of Co nanoparticles, thus enhancing its catalytic activity and stability in activating CaSO3 for water decontamination. The catalytic performance, kinetic research, influences of inorganic anions, pH, and degradation mechanism of chlortetracycline degradation catalyzed by the Co-NCNRs/CaSO3 system have been studied in detail. This work not only proposed a facile method for synthesis of nanoconfined catalyst but also provided an excellent Co-NCNRs/CaSO3 system for wastewater treatment.

La doping of CoFe Prussian blue analogs for improved catalytic activity toward norfloxacin degradation

Prussian blue analogs (PBAs) are promising catalysts in heterogeneous oxidation processes. The catalytic activity of PBAs relies on exposed crystal facets and accessible active sites on the PBA framework. Employing a heteroatom doping strategy using a rare earth element (La), we regulated the crystal structure and optimized the catalytic activity of CoFe PBA for peroxymonosulfate (PMS)-driven degradation of the antibiotic norfloxacin (NOR). The La atoms were mainly doped in the interstitial sites of the CoFe PBA cubic lattices, without affecting the electron distributions of Co and Fe metals or the face-centered cubic crystal phase of the coordination skeleton. La doping dominated the (111) and (100) as the main exposed facets of CoFeLa PBA, increasing the affinity of CoFeLa PBAs for PMS adsorption due to the higher surface energy of the two facets. Consequently, the activation energy considerably declined from 77.57 kJ/mol in CoFe PBA to 51.66 kJ/mol in CoFeLa PBA and the catalytic activity for PMS-driven NOR degradation was largely improved, which can reach 76.4 % removal of NOR within 15 min, with an increased initial rate constant k of 0.095 min−1. 1O2 was proven as the main reactive specie responsible for NOR degradation in the PMS/CoFeLa system, and O2·− and SO4·− were verified as the important intermediates to generate 1O2. Thus, La doping can effectively enhance the catalytic performance of PBA-based catalysts for organic pollutant removal.

Theory-guided unraveling of the mechanism underlying Cu1.0/Mn1.0-ZnO with dual reaction centers for enhanced peroxymonosulfate activation

Developing efficient catalytic systems for water contamination removal is a topic of great interest. However, the use of heterogeneous catalysts faces challenges due to insufficient active sites and electron cycling. In this study, results from first-principles calculations demonstrate that dual reaction centers (DRCs) are produced around the Cu and Mn sites in Cu1.0/Mn1.0-ZnO due to the electronegativity difference. Experimental results reveal the material with DRCs greatly enhances electron transfer efficiency and significantly impacts the oxidation and reduction of peroxymonosulfate (PMS). In addition, the self-consistent potential correction (SCPC) method was introduced to correct the energy and charge of charged periodic systems simulating a catalytic process, resulting in more precise catalytic results. Specifically, the material exhibits a preference for adsorbing negatively charged PMS anions at electron-deficient Mn sites, facilitating PMS oxidation for the generation of 1O2, and PMS reduction around the electron-rich Cu for the formation of •OH and SO4•−. The major reactive oxygen species is 1O2, showcasing effective performance in various degradation systems. Overall, our work provides novel insights into the persulfate-based heterogeneous catalytic oxidation process, paving the way for the development of high-performance catalytic systems for water purification.

Metal-Free Activation of Molecular Oxygen by 9-Fluorenone-Based Porous Organic Polymers for Selective Aerobic Oxidation.

Oxygen activation is a critical step in heterogeneous oxidative processes, particularly in catalytic, electrolytic, and pharmaceutical applications. Among the various catalysts available for photocatalytic O2 activation, homogeneous aryl ketones are at the forefront. To avoid the degradation and deactivation of aryl ketones, 9-fluorenone-based porous organic polymers were designed and regulated by doping them with co-monomers. The obtained heterogeneous photocatalyst showed good performance in O2 activation, and its performance was better than that of homogeneous 9-fluorenone. The obtained heterogeneous photocatalyst showed good reusability. We believe that the presented method and findings represent an important step toward designing catalysts tailored for specific tasks.

Metal‐Free Activation of Molecular Oxygen by 9‐Fluorenone‐Based Porous Organic Polymers for Selective Aerobic Oxidation

AbstractOxygen activation is a critical step in heterogeneous oxidative processes, particularly in catalytic, electrolytic, and pharmaceutical applications. Among the various catalysts available for photocatalytic O2 activation, homogeneous aryl ketones are at the forefront. To avoid the degradation and deactivation of aryl ketones, 9‐fluorenone‐based porous organic polymers were designed and regulated by doping them with co‐monomers. The obtained heterogeneous photocatalyst showed good performance in O2 activation, and its performance was better than that of homogeneous 9‐fluorenone. The obtained heterogeneous photocatalyst showed good reusability. We believe that the presented method and findings represent an important step toward designing catalysts tailored for specific tasks.

Correlating active sites and oxidative species in single-atom catalyzed Fenton-like reactions.

Single-atom catalysts (SACs) have gained widespread popularity in heterogeneous catalysis-based advanced oxidation processes (AOPs), owing to their optimal metal atom utilization efficiency and excellent recyclability by triggering reactive oxidative species (ROS) for target pollutant oxidation in water. Systematic summaries regarding the correlation between the active sites, catalytic activity, and reactive species of SACs have rarely been reported. This review provides an overview of the catalytic performance of carbon- and metal oxide-supported SACs in Fenton-like reactions, as well as the different oxidation pathways induced by the metal and non-metal active sites, including radical-based pathways (e.g., ·OH and SO4˙-) and nonradical-based pathways (e.g. 1O2, high-valent metal-oxo species, and direct electron transfer). Thereafter, we discuss the effects of metal types, coordination environments, and spin states on the overall catalytic performance and the generated ROS in Fenton-like reactions. Additionally, we provide a perspective on the future challenges and prospects for SACs in water purification.

Effect of log Kow on the degradation of pharmaceutically active compounds in a heterogeneous catalytic persulfate activation system

In heterogeneous catalytic advanced oxidation processes (HC-AOP), enhancing the reaction rate is the biggest challenge. To enhance the reaction rate, it is necessary to increase the mass transfer rate of reactants toward the catalyst surface and the number of active sites that will provide better contact with the reactants and higher mass transfer. The hydrophobicity of the reactant is an important parameter that affects the transport of molecules toward solid surfaces. In this study, the effect of log Kow, an indicator of hydrophobicity, on enhancing the catalytic activity in persulfate (PS) activation for pharmaceutic compounds (PCs) degradation was investigated. For this purpose, some PCs with different log Kow were selected and their adsorption and degradation behaviors were investigated depending on the PS concentration, catalyst dosage, contact time, pH, and temperature in HC-AOP. Adsorption percentages increased significantly with increasing log Kow value. PCs with higher log Kow were completely degraded at the end of the shorter contact times in the presence of lower catalyst and PS. PCs were significantly degraded by the triple catalytic effect of AC, Fe, and temperature. The pseudo-first-order kinetic model was the best fit for the degradation reaction for all PCs. The higher apparent rate constants and lower activation energy values of the PCs belonging to high log Kow confirmed that log Kow is an effective parameter in enhancing the catalytic activity.

Enhanced chalcopyrite-catalyzed heterogeneous Fenton oxidation of diclofenac by ABTS

The widely used 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) has gained growing attention in advanced oxidation processes (AOPs), whereas there was limited knowledge regarding the feasibility of ABTS in enhancing heterogeneous Fenton oxidation so far. Hereof, ABTS was introduced into the chalcopyrite (CuFeS2)- catalyzed heterogeneous Fenton oxidation process to degrade diclofenac (DCF), and the degradation efficiency was enhanced by 25.5% compared with CuFeS2/H2O2 process. The available reactive oxygen species (ROS) and the enhanced mechanism were elaborated. Experimental results uncovered that •OH was the dominant reactive species responsible for the DCF degradation in the CuFeS2/H2O2/ABTS process, and ABTS•+ was derived from both •OH and Fe(IV). The presence of ABTS contributed significantly to the redox cycle of surface Fe of CuFeS2, and the roles of reductive sulfur species and surface Cu(I) in promoting surface Fe cycling also could not be neglected. In addition, the effects of several influencing factors were considered, and the potential practicability of this oxidation process was examined. The results demonstrate that the CuFeS2/H2O2/ABTS process would be a promising approach for water purification. This study will contribute to the development of enhancing strategies using ABTS as a redox mediator for heterogeneous Fenton oxidation of pharmaceuticals.

Enhanced Oxidation of Organic Compounds by the Ferrihydrite-Ferrate System: The Role of Intramolecular Electron Transfer and Intermediate Iron Species.

Previous studies mostly held that the oxidation capacity of ferrate depends on the involvement of intermediate iron species (i.e., FeIV/FeV), however, the potential role of the metastable complex was disregarded in ferrate-based heterogeneous catalytic oxidation processes. Herein, we reported a complexation-mediated electron transfer mechanism in the ferrihydrite-ferrate system toward sulfamethoxazole (SMX) degradation. A synergy between intermediate FeIV/FeV oxidation and the intramolecular electron transfer step was proposed. Specifically, the conversion of phenyl methyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO2) suggested that FeIV/FeV was involved in the oxidation of SMX. Moreover, based on the in situ Raman test and chronopotentiometry analysis, the formation of the metastable complex of ferrihydrite/ferrate was found, which possesses higher oxidation potential than free ferrate and could achieve the preliminary oxidation of organics via the electron transfer step. In addition, the amino group of SMX could complex with ferrate, and the resulting metastable complex of ferrihydrite/ferrate would combine further with SMX molecules, leading to intramolecular electron transfer and SMX degradation. The ferrate loss experiments suggested that ferrihydrite could accelerate the decomposition of ferrate. Finally, the effects of pH value, anions, humic acid, and actual water on the degradation of SMX by ferrihydrite-ferrate were also revealed. Overall, ferrihydrite demonstrated high catalytic capacity, good reusability, and nontoxic performance for ferrate activation. The ferrihydrite-ferrate process may be a green and promising method for organic removal in wastewater treatment.

Carbon nitride with a tailored electronic structure toward peroxymonosulfate activation: A direct electron transfer mechanism for organic pollutant degradation

The persulfate-based nonradical reaction process has gained increasing attention in removing organic contaminants, and the process dramatically needs affordable, robust, high-performance heterogeneous catalysts. Herein, dimethyl formamide (DMF) incorporated graphitic carbon nitride (DCN) was synthesized. The molecular engineering of the heptazine unit in DCN improves the electron mobility, strengthens the built-in electric field, and provides abundant active sites, thus enabling DCN to efficiently activate PMS for organic degradation, with 100 % removal of BPA within 12 min. The investigation of the reactive species and electrochemical properties confirmed the direct electron transfer in the PMS activation for organic degradation over DCN. More importantly, DCN can be used as a membrane catalyst in a flowing catalytic unit, enabling continuous water purification and catalyst regeneration. This work provides novel guidance for metal-free catalyst design and profound insights into the persulfate-based heterogeneous catalytic oxidation process for water decontamination technology.

Carbon nitride nanotubes anchored with Cu(I) triggers peracetic acid activation with visible light for removal of antibiotic contaminants: Probing mechanisms of non-radical pathways and identifying active sites

The peracetic acid (PAA)-activation process has attracted much attention in wastewater treatment. However, the low electron efficiency at the interface between heterogeneous catalysts and PAA has affected its practical application. For this study, we developed a carbon nitride hollow-nanotube catalysts with dispersed Cu(I) sites (Cu(I)-TCN) for the photocatalytic activation of PAA for antibiotics degradation. The obtained Cu(I)-TCN catalyst demonstrated an enhanced capacity for visible light harvesting along with increased charge transfer rates. Specifically, the developed Cu(I)-TCN/visible light/PAA system was able to completely remove antibiotics within 20 min, with a kinetic constant that was 25 times higher than a Cu(I)-TCN/visible light system, and 83 times higher than Cu(I)-TCN/PAA systems. Scavenging experiment and electron paramagnetic resonance (EPR) indicated that singlet oxygen was dominant reactive specie for sulfisoxazole (SIZ) removal. Besides, electrochemical tests and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy verified that the electron transfer efficiency of PAA activation was promoted due to the formation of inner-sphere interactions between PAA and Cu(I)-TCN, resulting in the quick removal of antibiotics. Further, after exposure to visible light, the Cu(I)-TCN excited photogenerated electrons which supplemented the electrons consumed in the reaction and drove the valence cycle of Cu ions. Overall, this research offered novel insights into the non-radical pathway for heterogeneous visible light-driven advanced oxidation processes and their potential for practical wastewater remediation.

Competitive study of homogeneous and heterogeneous Fenton-like flow-through propoxur oxidation in ROC solution.

Reverse osmosis is used as a tertiary treatment for wastewater reclamation. However, sustainable management of the concentrate (ROC) is challenging, due to the need for treatment and/or disposal. The objective of this research was to investigate the efficiency of homogeneous and heterogeneous Fenton-like oxidation processes in removing propoxur (PR), a micro-pollutant compound, from synthetic ROC solution in a submerged ceramic membrane reactor operated in a continuous mode. A freshly prepared amorphous heterogeneous catalyst was synthesized and characterized, revealing a layered porous structure of 5-16 nm nanoparticles that formed aggregates (33-49 μm) known as ferrihydrite (Fh). The membrane exhibited a rejection of >99.6% for Fh. The homogeneous catalysis (Fe3+) exhibited better catalytic activity than the Fh in terms of PR removal efficiencies. However, by increasing the H2O2 and Fh concentrations at a constant molar ratio, the PR oxidation efficiencies were equal to those catalyzed by the Fe3+. The ionic composition of the ROC solution had an inhibitory effect on the PR oxidation, whereas increased residence time improved it up to 87% at a residence time of 88 min. Overall, the study highlights the potential of heterogeneous Fenton-like processes catalyzed by Fh in a continuous mode of operation.