Embedding electronic perpetual motion into single-atom catalysts for persistent Fenton-like reactions.

In our quest to leverage the capabilities of the emerging single-atom catalysts (SACs) for wastewater purification, we confronted fundamental challenges related to electron scarcity and instability. Through meticulous theoretical calculations, we identified optimal placements for nitrogen vacancies (Nv) and iron (Fe) single-atom sites, uncovering a dual-site approach that significantly amplified visible-light absorption and charge transfer dynamics. Informed by these computational insights, we cleverly integrated Nv into the catalyst design to boost electron density around iron atoms, yielding a potent and flexible photoactivator for benign peracetic acid. This exceptional catalyst exhibited remarkable stability and effectively degraded various organic contaminants over 20 cycles with self-cleaning properties. Specifically, the Nv sites captured electrons, enabling their swift transfer to adjacent Fe sites under visible light irradiation. This mechanism accelerated the reduction of the formed "peracetic acid-catalyst" intermediate. Theoretical calculations were used to elucidate the synergistic interplay of dual mechanisms, illuminating increased adsorption and activation of reactive molecules. Furthermore, electron reduction pathways on the conduction band were elaborately explored, unveiling the production of reactive species that enhanced photocatalytic processes. A six-flux model and associated parameters were also applied to precisely optimize the photocatalytic process, providing invaluable insights for future photocatalyst design. Overall, this study offers a molecule-level insight into the rational design of robust SACs in a photo-Fenton-like system, with promising implications for wastewater treatment and other high-value applications.

Customizing Cerium Oxide Particle Synthesis with Hybrid Polyion Complex Templates for Enhanced Oxidation Performance in Photo-Fenton Processes.

Hybrid poly-ion complexes were synthesized through the complexation of a double hydrophilic copolymer with Ce(III) ions. These colloids act as reservoirs for cerium ions, enabling the synthesis of cerium-based Prussian blue nanoparticles with a cubic structure, a narrow size distribution around 100 nm, and good colloidal stability in water. Upon high-temperature calcination, these nanoparticles are transformed into a cerium/iron-based metal oxide catalyst (CeO2/Fe2O3). The resultant composite catalyst demonstrates superior performance in the photo-Fenton oxidation of methylene blue pollutants, achieving a conversion efficiency that rivals other metal-based oxides and cerium-based catalysts.

Fenton-Like Reaction: Recent Advances and New Trends.

The Fenton reaction refers to the reaction in which ferrous ions (Fe2+) produce hydroxyl radicals and other reactive oxidizing substances by decomposing hydrogen peroxide (H2O2). This paper reviews the mechanism, application system, and materials employed in the Fenton reaction including conventional homogeneous and non-homogeneous Fenton reactions as well as photo-, electrically-, ultrasonically-, and piezoelectrically-triggered Fenton reactions, and summarizes the applications in the degradation of soil oil pollutions, landfill leachate, textile wastewater, and antibiotics from a practical point of view. The mineralization paths of typical pollutant are elucidated with relevant case studies. The paper concludes with a summary and outlook of the further development of Fenton-like reactions.

Epoxiconazole degradation in water samples: a comparative study of Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis processes.

Epoxiconazole (EPO) is classified as a persistent organic pollutant due to its ability to persist in the environment for prolonged periods. Its degradation is pivotal in mitigating its environmental impact. This investigation focuses on assessing the degradation of EPO using various methodologies, namely Fenton, photo-Fenton, solar photo-Fenton, and solar photolysis, conducted in both Milli-Q water and groundwater. These experiments encompassed evaluations at both the standard pH typically used in photo-Fenton reactions and the natural pH levels inherent to the respective aqueous environments. Additionally, EPO degradation products were analyzed after a 60-min reaction. Notably, in systems utilizing groundwater, the inclusion of additional iron was unnecessary, as the naturally occurring iron content in the groundwater facilitated the intended processes. Specifically, in Milli-Q water, solar photo-Fenton demonstrated an EPO degradation efficiency of 97%. Furthermore, the substitution of Milli-Q water with groundwater in Fenton-like processes did not significantly affect the efficacy of EPO degradation. These findings underscore the potential of solar photo-Fenton as an economically viable and environmentally sustainable strategy for EPO degradation.

New Insights into Photo-Fenton Chemistry: The Overlooked Role of Excited IronIII Species.

Direct photoreduction of FeIII is a widely recognized route for accelerating FeIII/FeII cycle in photo-Fenton chemistry. However, most of the wavelengths covering the full spectral range are insufficient to supply enough photon energy for the direct reduction process. Herein, the hitherto neglected mechanism of FeIII reduction that the FeIII indirect reduction pathway initiated by light energy-dependent reactivity variation and reactive excited state (ES) was explored. Evolution of excited-state FeIII species (*FeIII) resulting from metal-centered charge excitation (MCCE) of FeIII is experimentally verified using pulsed laser femtosecond transient absorption spectroscopy with UV-vis detection and theoretically verified by quantum chemical calculation. Intense photoinduced intravalence charge transition was observed at λ = 380 and 466 nm, revealing quartet 4MCCE and doublet 2MCCE and their exponential processes. Light energy-dependent variation of *FeIII reactivity was kinetically certified by fitting the apparent rate constant of the radical-chain sequence of photo-Fenton reactions. Covalency is found to compensate for the intravalence charge separation following photoexcitation of the metal center in the MCCE state of Fenton photosensitizer. The *FeIII is established as a model, demonstrating the intravalence hole delocalization in the ES can be leveraged for photo-Fenton reaction or other photocatalytic schemes based on electron transfer chemistry.

Z-scheme heterojunction composed of Fe-doped g-C3N4 and Bi2MoO6 for photo-fenton degradation of antibiotics over a wide pH range: Activity and toxicity assessment.

In photo-Fenton technology, the narrower pH range limits its practical application for antibiotic wastewater remediation. Therefore, in this study, a Z-scheme heterojunction photo-Fenton catalyst was constructed by Fe-doped graphite-phase carbon nitride in combination with bismuth molybdate for the degradation of typical antibiotics. Fe doping can shorten the band gap and increase visible-light absorption. Simultaneously, the constructed Z-scheme heterojunction provides a better charge transfer pathway for the photo-Fenton reaction. Within 30 min, Fe3CN/BMO-3 removed 95.54% of tetracycline hydrochloride (TC), and its remarkable performance was the higher Fe3+/Fe2+ conversion efficiency through the decomposition of H2O2. The Fe3CN/BMO-3 catalyst showed remarkable photo-Fenton degradation performance in a wide pH range (3.0-11.0), and it also had good stability in the treatment of TC wastewater. Furthermore, the order of action of the active species was h+ > ·O2- > 1O2 > ·OH, and the toxicity assessment suggested that Fe3CN/BMO-3 was effective in reducing the biotoxicity of TC. The catalyst proved to be an economically feasible and applicable material for antibiotic photo-Fenton degradation, and this study provides another perspective on the application of elemental doping and constructed heterojunction photo-Fenton technology for antibiotic water environmental remediation.

Enhanced degradation of enoxacin using ferrihydrite-catalyzed heterogeneous photo-Fenton process.

The ferrihydrite-catalyzed heterogeneous photo-Fenton reaction shows great potential for environmental remediation of fluoroquinolone (FQs) antibiotics. The degradation of enoxacin, a model of FQ antibiotics, was studied by a batch experiment and theoretical calculation. The results revealed that the degradation efficiency of enoxacin reached 89.7% at pH 3. The hydroxyl radical (∙OH) had a significant impact on the degradation process, with a cumulative concentration of 43.9 µmol L-1 at pH 3. Photogenerated holes and electrons participated in the generation of ∙OH. Eleven degradation products of enoxacin were identified, with the main degradation pathways being defluorination, quinolone ring and piperazine ring cleavage and oxidation. These findings indicate that the ferrihydrite-catalyzed photo-Fenton process is a valid way for treating water contaminated with FQ antibiotics.

FeOCl/MOF-derived In2S3 photocatalysts with high H2O2 adsorption: Degradation mechanism, H2O2 activation process.

The FeOCl-based photo-Fenton heterojunction catalyst holds great promise for effective water pollution treatment. A novel heterojunction FeOCl/MOF-In2S3 (F/M-I) was fabricated by coating hollow MOF-In2S3 nanoflowers onto the surface of FeOCl. Under the optimal conditions, the maximum photo-Fenton degradation rate constants of FeOCl/MOF-In2S3 for oxytetracycline (OTC) within 20 min is 0.88192 L mg-1·min-1, which are 3.2 and 2.5 times that of pure FeOCl (0.27357 L mg-1·min-1) and MOF-In2S3 (0.35222 L mg-1·min-1). Density functional theory (DFT) results confirm that the electron-rich nature of MOF-In2S3 accelerates the cycle between Fe (III)/Fe (II)of FeOCl, promoting H2O2 adsorption by FeOCl/MOF-In2S3 and generating more hydroxyl radicals (·OH) for pollutant degradation. Based on the results of DFT, combined with the results of the reactive oxidation species scavenger (ROSs), electron paramagnetic resonance (EPR) and Mott-Schottky curves, the separation and transfer behavior of photoexcited charges in FeOCl/MOF-In2S3 heterojunction and the possible photocatalytic degradation mechanism were investigated. Finally, a Z-scheme heterostructure is proposed to elucidate the catalytic mechanism. This study provides a new perspective on designing and synthesizing semiconductor materials for water treatment by photo-Fenton catalysis.

Z-scheme Fe@Fe2O3/BiOBr heterojunction with efficient carrier separation for enhanced heterogeneous photo-Fenton activity of tetracycline degradation: Fe2+ regeneration, mechanism insight and toxicity evaluation.

The recombination of photogenerated carrier leads to inefficient Fe2+ regeneration, which limits the extensive application of heterogeneous photo-Fenton. Here, a novel Fe@Fe2O3/BiOBr catalyst with Z-scheme heterojunction structure is designed, and the establishment of the Z-scheme heterojunction facilitates the separation and transfer of photogenerated carrier and maintains the superior redox capability of the system. As-prepared Fe@Fe2O3/BiOBr catalyst exhibits outstanding catalytic performance and stability, especially for the optimum composite FFB-3, its degradation efficiency of tetracycline (TC) achieves 98.22% and the mineralization degree reaches 59.48% within 90 min under natural pH. The preeminent catalytic efficiency benefited from the synergistic of heterogeneous photo-Fenton and Z-scheme carriers transfer mechanism, where Fe2+ regeneration was achieved by photogenerated electrons, and increased hydroxyl radicals were produced with the participation of H2O2 in-situ generated. The results of free-radical scavenging experiment and ESR illustrated that •OH, •O2-, 1O2 and h+ were active species participating in TC degradation. Furthermore, the TC degradation paths were proposed according to LC-MS, and the toxicity evaluation result showed that the toxicity of TC solutions was markedly decreased after degradation. This study provides an innovative strategy for heterogeneous photo-Fenton degradation of antibiotic contaminations by constructing Z-scheme heterojunctions.

Degradation of phenol in wastewater through an integrated dielectric barrier discharge and Fenton/photo-Fenton process.

In this study, a non-thermal dielectric barrier discharge-Fenton/photo-Fenton process was investigated to remove phenol from synthetic wastewater. The changes and optimal values of influencing parameters, including treatment time, iron concentration, phenol initial concentration, and pH, were investigated based on the central composite design (CCD) method. The presence of 0.4 mmol/L of iron in the phenol solution with a concentration of 100 mg/L increased the removal efficiency and pseudo-first-order kinetic constant compared to dielectric barrier discharge cold plasma (DBDP) alone from 0.0824 min-1 and 56.8% to 0.2078 min-1 and 86.83%, respectively. The phenol removal efficiency was reduced to 52.9%, 45.6% and 31.8% by adding tert-butyl alcohol (TBA) with concentrations of 50, 100, and 200 mg/l, respectively. After 12 min of DBDP irradiation, the pH of the sample decreased from 5.95 to 3.42, and the temperature of the sample increased from 19.3 to 37.2 degrees Celsius. The chemical oxygen demand (COD) of the sample containing 100 mg/L phenol under plasma-Fenton/photo-Fenton irradiation decreased from 241 mg/L to 161 mg/L. Phenol removal efficiency after 10 min of treatment in the presence of 0.4 mmol/L of iron with the reactor volume of 50 mL was 87%, but the efficiency decreased to 76%, 47%, and 9% by increasing the volume to 100, 200, and 400 mL, respectively. Reducing the power led to a decrease in the removal efficiency from 56.8% for 100 W power to 10.8% for 40 W. The energy efficiency for 50% removal by DBDP and plasma-Fenton/photo-Fenton systems was 5.86×10-3 kWh/mg and 1.27×10-3 kWh/mg, respectively.

Enhanced H2O2 Upcycling into Hydroxyl Radicals with GO/Ni:FeOOH-Coated Silicon Nanowire Photocatalysts for Wastewater Treatment.

There remains continued interest in improving the advanced water oxidation process [e.g., ultraviolet (UV)/hydrogen peroxide (H2O2)] for more efficient and environmentally friendly wastewater treatment. Here, we report the design, fabrication, and performance of graphene oxide (GO, on top)/nickel-doped iron oxyhydroxide (Ni:FeOOH, shell)/silicon nanowires (SiNWs, core) as a new multifunctional photocatalyst for the degradation of common pollutants like polystyrene and methylene blue through enhancing the hydroxyl radical (•OH) production rate of the UV/H2O2 system. The photocatalyst combines the advantages of a large surface area and light absorption characteristics of SiNWs with heterogeneous photo-Fenton active Ni:FeOOH and photocatalytically active/charge separator GO. In addition, the built-in electric field of GO/Ni:FeOOH/SiNWs facilitates the charge separation of electrons to GO and holes to Ni:FeOOH, thus boosting the photocatalytic performance. Our photocatalyst increases the •OH yield by 5.7 times compared with that of a blank H2O2 solution sample and also extends the light absorption spectrum to include visible light irradiation.

Carbon defects-enriched NBC-C3N5@CoMn with ultrafast modulation of redox couples for efficient degradation of contaminant.

The inefficiency of catalysts in sulfate radical-based advanced oxidation processes (SR-AOPs) is primarily attributed to the sluggish circulation of redox couples. Herein, a carbon defects-enriched NBC-C3N5@CoMn (NCC) was synthesized through a self-assembly approach. The carbon defects within the NCC induce the electron trap effect, thereby facilitating the efficient cycling of redox couples in photo-Fenton-like processes during contaminant degradation. This effect enables the self-regeneration of the NCC catalyst. The reductive redox couples (Co (II) and Mn (II)) are continuously regenerated following the degradation process. Within the NCC, CoMn layered double hydroxides (LDHs) act as primary active sites, promoting the generation of hydroxyl radicals (•OH), sulfate radicals (SO4•-) and singlet oxygen (1O2) through continuous electron gain and loss. Additionally, the internal electric field established within the NCC further accelerates electron transfer. Density Functional Theory (DFT) calculations confirm that the carbon defects-enriched NCC exhibits lower adsorption energies and higher electron transfer efficiencies than carbon defect-deficient NCC. This study introduces a novel photocatalyst with self-regenerating capabilities, presenting an innovative approach to regulate redox couples in SR-AOPs for sustainable degradation.

Construction of self-cleaning g-C3N4/Bi2MoO6/PVDF membrane and coupling with photo-Fenton-like reaction for sustainable removal of antibiotics in wastewater.

Constructing a photocatalytic membrane and photo-Fenton reaction coupling system is a novel strategy to enhance the photocatalytic activity of the membrane and eliminate the problem of membrane contamination. Herein, a g-C3N4/Bi2MoO6/PVDF photocatalytic membrane was prepared using a tannic acid-assisted in-situ deposition method. The membrane was characterized by three advantages of photocatalytic, self-cleaning, and antibacterial properties. Under the photo-Fenton-like conditions, the membrane had superior photodegradation efficiency of 90.7% for tetracycline, one of the main antibiotic contaminants in the China's aquatic system. Moreover, the membrane had excellent photo-Fenton self-cleaning ability, its flux recovery rate was up to 96%-98% after the self-cleaning process. Photoluminescence spectra, diffuse UV-visible spectrum, transient photocurrent responses, and electrochemical AC impedance spectrum results show that the heterojunction structure formed by g-C3N4 and Bi2MoO6 could improve the separation efficiency of photogenerated electrons-hole pairs. Electron spin resonance spectroscopy confirmed the photo-electrons facilitated the formation of hydroxyl radical (·OH) in the existence of H2O2, which enhanced tetracycline degradation. Moreover, the superior photo-Fenton self-cleaning performance, which mainly relied on the active free radicals produced by the photo-Fenton-like membrane to remove dirt on the membrane surface or in the membrane pore channel. Our results may shed new light on the development of promising photocatalytic membrane systems by coupling with photo-Fenton-like processes, and facilitate their applications for wastewater treatment.

Synthesis of 3D Sb2O3-based heterojunction reinforced by SPR effect and photo-Fenton mechanism for upgraded oxidation of metronidazole in water environments.

The traditional homogenous and heterogenous Fenton reactions have frequently been restrained by the lower production of Fe2+ ions, which significantly obstructs the generation of hydroxyl radicals from the decomposition of H2O2. Thus, we introduce novel photo-Fenton-assisted plasmonic heterojunctions by immobilizing Fe3O4 and Bi nanoparticles onto 3D Sb2O3 via co-precipitation and solvothermal approaches. The ternary Sb2O3/Fe3O4/Bi composites offered boosted photo-Fenton behavior with a metronidazole (MNZ) oxidation efficiency of 92% within 60 min. Among all composites, the Sb2O3/Fe3O4/Bi-5% hybrid exhibited an optimum photo-Fenton MNZ reaction constant of 0.03682 min- 1, which is 5.03 and 2.39 times higher than pure Sb2O3 and Sb2O3/Fe3O4, respectively. The upgraded oxidation activity was connected to the complementary outcomes between the photo-Fenton behavior of Sb2O3/Fe3O4 and the plasmonic effect of Bi NPs. The regular assembly of Fe3O4 and Bi NPs enhances the surface area and stability of Sb2O3/Fe3O4/Bi. Moreover, the limited absorption spectra of Sb2O3 were extended into solar radiation by the Fe3+ defect of Fe3O4 NPs and the surface plasmon resonance (SPR) effect of Bi NPs. The photo-Fenton mechanism suggests that the co-existence of Fe3O4/Bi NPs acts as electron acceptor/donor, respectively, which reduces recombination losses, prolongs the lifetime of photocarriers, and produces more reactive species, stimulating the overall photo-Fenton reactions. On the other hand, the photo-Fenton activity of MNZ antibiotics was optimized under different experimental conditions, including catalyst loading, solution pH, initial MNZ concentrations, anions, and real water environments. Besides, the trapping outcomes verified the vital participation of •OH, h+, and •O2- in the MNZ destruction over Sb2O3/Fe3O4/Bi-5%. In summary, this work excites novel perspectives in developing boosted photosystems through integrating the photocatalysis power with both Fenton reactions and the SPR effects of plasmonic materials.

Establishing an affordable solar-floating Fe2O3@A1-xRx-TiO2 photo-Fenton catalytic system through the cyclic utilization of iron waste to de-pollute textile water contamination.

This study focuses on developing a cost-effective Fe2O3 catalyst from oilfield iron waste to create a floating heterogeneous photo-Fenton system with anatase/rutile(A/R) TiO2 heterophase photocatalyst (cork-Fe2O3@A1-xRx-TiO2) for treating textile pollution in sunlight. Through controlling sol-gel (SG) microwave heating technique, the A/R ratio of A1-xRx-TiO2 crystal is tuned (A/R ratio = 1.13 and Eg = 3.02 eV) to improve adsorption-photocatalytic removal of anionic/cationic dyes with an apparent kinetic rate (kapp) of 0.0074 min-1 under UV-visible irradiation. The developed cork-Fe2O3@A53.1R46.8-TiO2 floated system also outperforms the classical photo-Fenton with Fe/H2O2 benchmark, showing a 2-fold enhancement in textile dye degradation (kapp = 0.216 min-1 and space-time yield (SY) of 1.7*10-4 mol/E.g at pH 5.65) with high stability over four reuse cycles. The formation of Fe2O3@A53.1R46.8-TiO2 Type-II heterojunction is confirmed by optical and electrochemical analyses, allowing the acceleration of direct electron transfer mechanism and oxidative degradation of dyes during photo-Fenton reaction. As a case study, the cork-Fe2O3@A53.1R46.8-TiO2 system demonstrates a high capability for efficient mineralization of textile pollution in a real effluent, achieving 82 ± 2% reduction in the total organic contents at an operational cost of 2.61 $/kg.m3 in sunlight. Thus, this research addresses challenges in conventional Fenton chemistry, iron waste recycling, and catalyst retention, offering new insights for sustainable treatment of textile effluents and environmental protection.

Development of an artificial neural network (ANN) for the prediction of a pilot scale mobile wastewater treatment plant performance.

Productive activities such as pig farming are a fundamental part of the economy in Mexico. Unfortunately, because of this activity, large quantities of wastewater are generated that have a negative impact in the environment. This work shows an alternative for treating piggery wastewater based on advanced oxidation processes (Fenton and solar photo Fenton, SPF) that have been probed successfully in previous works. In the first stage, Fenton and SPF were carried out on a laboratory scale using a Taguchi L9-type experimental design. From the statistical analysis of this design, the operating parameters: pH, time, hydrogen peroxide concentration [H2O2], and iron ferrous concentration [Fe2+] that maximize the response variables: Chemical Oxygen Demand (COD), Total Organic Carbon (TOC), and color were chosen. From these, a cascade forward neural network was implemented to establish a correlation between data from the variables to the physicochemical parameters to be measure being that a great fit of the data was obtained having a correlation coefficient of 0.99 which permits to optimize the pollutant degradation and predict the removal efficiencies at pilot scale but with a projection to a future industrial scale. A relevant result, it was found that the optimal values for maximizing the removal of physicochemical parameters were pH = 3, time = 60 min, H2O2/COD = 1.5 mg L-1, and H2O2/Fe2+ = 2.5 mg L-1. With these conditions degradation percentages of 91.44%, 47.14%, and 97.89% for COD, TOC, and color were obtained from the Fenton process, while for SPF the degradation percentage increased moderately. From the ANN analysis, the possibility to establish an intelligent system that permits to predict multiple results from operational conditions has been achieved.

Broad Spectral Response FeOOH/BiO2-x Photocatalyst with Efficient Charge Transfer for Enhanced Photo-Fenton Synergistic Catalytic Activity.

In this work, to promote the separation of photogenerated carriers, prevent the catalyst from photo-corrosion, and improve the photo-Fenton synergistic degradation of organic pollutants, the coating structure of FeOOH/BiO2-x rich in oxygen vacancies was successfully synthesized by a facile and environmentally friendly two-step process of hydrothermal and chemical deposition. Through a series of degradation activity tests of synthesized materials under different conditions, it was found that FeOOH/BiO2-x demonstrated outstanding organic pollutant degradation activity under visible and near-infrared light when hydrogen peroxide was added. After 90 min of reaction under photo-Fenton conditions, the degradation rate of Methylene Blue by FeOOH/BiO2-x was 87.4%, significantly higher than the degradation efficiency under photocatalysis (60.3%) and Fenton (49.0%) conditions. The apparent rate constants of FeOOH/BiO2-x under photo-Fenton conditions were 2.33 times and 3.32 times higher than photocatalysis and Fenton catalysis, respectively. The amorphous FeOOH was tightly coated on the layered BiO2-x, which significantly increased the specific surface area and the number of active sites of the composites, and facilitated the improvement of the separation efficiency of the photogenerated carriers and the prevention of photo-corrosion of BiO2-x. The analysis of the mechanism of photo-Fenton synergistic degradation clarified that ·OH, h+, and ·O2- are the main active substances involved in the degradation of pollutants. The optimal degradation conditions were the addition of the FeOOH/BiO2-x composite catalyst loaded with 20% Fe at a concentration of 0.5 g/L, the addition of hydrogen peroxide at a concentration of 8 mM, and an initial pH of 4. This outstanding catalytic system offers a fresh approach to the creation and processing of iron-based photo-Fenton catalysts by quickly and efficiently degrading various organic contaminants.

High-Efficiency Photo-Fenton-like Catalyst of FeOOH/g-C3N4 for the Degradation of PNP: Characterization, Catalytic Performance and Mechanism Exploration.

The composite photocatalyst FeOOH/g-C3N4 was prepared through thermal polycondensation and co-precipitation methods, followed by XRD, SEM and UV-vis characterization. The stability of FeOOH/g-C3N4 was explored by the recycling test. The active species in the reaction system were investigated by the capture experiment. The results indicated that the optimal preparation condition for g-C3N4 involved calcination at 600 °C for 4 h. XRD analysis revealed that g-C3N4 exhibits a high-purity phase, and Fe in FeOOH/g-C3N4 exists in a highly dispersed amorphous state. SEM analysis showed that FeOOH/g-C3N4 has a rough surface with an irregular layered structure. Element composition analysis confirmed that the content of elements in the prepared catalyst is consistent with the theoretical calculation. FeOOH/g-C3N4 possesses the largest specific surface area of 143.2 m2/g and a suitable pore distribution. UV-vis DRS analysis showed that the absorption intensity of FeOOH/g-C3N4 is stronger than that of g-C3N4. When the catalyst dosage was 1.0 g/L, the H2O2 dosage was 4 mmol/L, the PNP initial concentration was 10 mg/L and the initial pH value was 5, the PNP removal could reach 92% in 120 min. Even after 5 cycles, the efficiency of PNP removal by FeOOH/g-C3N4 remains nearly 80%. The capture experiment indicated that both •OH and •O2- play roles in the photocatalytic degradation of PNP, with •OH being more significant. These findings affirm that FeOOH has been successfully incorporated into g-C3N4, resulting in a conspicuous catalytic effect on the degradation of PNP in the visible light-assisted Fenton-like reaction.

Double-Shelled Porous g-C3 N4 Nanotubes Modified with Amorphous Cu-Doped FeOOH Nanoclusters as 0D/3D Non-Homogeneous Photo-Fenton Catalysts for Effective Removal of Organic Dyes.

Graphite phased carbon nitride (g-C3 N4 ) has attracted extensive attention attributed to its non-toxic nature, remarkable physical-chemical stability, and visible light response properties. Nevertheless, the pristine g-C3 N4 suffers from the rapid photogenerated carrier recombination and unfavorable specific surface area, which greatly limit its catalytic performance. Herein, 0D/3D Cu-FeOOH/TCN composites are constructed as photo-Fenton catalysts by assembling amorphous Cu-FeOOH clusters on 3D double-shelled porous tubular g-C3 N4 (TCN) fabricated through one-step calcination. Combined density functional theory (DFT) calculations, the synergistic effect between Cu and Fe species could facilitate the adsorption and activation of H2 O2 , and the separation and transfer of photogenerated charges effectively. Thus, Cu-FeOOH/TCN composites acquire a high removal efficiency of 97.8%, the mineralization rate of 85.5% and a first-order rate constant k = 0.0507 min-1 for methyl orange (MO) (40 mg L-1 ) in photo-Fenton reaction system, which is nearly 10 times and 21 times higher than those of FeOOH/TCN (k = 0.0047 min-1 ) and TCN (k = 0.0024 min-1 ), respectively, indicating its universal applicability and desirable cyclic stability. Overall, this work furnishes a novel strategy for developing heterogeneous photo-Fenton catalysts based on g-C3 N4 nanotubes for practical wastewater treatment.

Application of Fe(III)-EDDS complexes and soybean peroxidase in photo-Fenton processes for organic pollutant removal: insights into possible synergistic effects.

Photo-Fenton processes activated by biodegradable Fe(III)-EDDS complexes have attracted huge attention from the scientific community, but the operative mechanism of the photo-activation of H2O2 in the presence of Fe(III)-EDDS has not been fully clarified yet. The application of the Fe(III)-EDDS complex in Fenton and photo-Fenton (mainly under UV-B light) processes, using 4-chlorophenol (4-CP) as a model pollutant was explored to give insights into the operative mechanism. Furthermore, the potential synergistic contribution of soybean peroxidase (SBP) was investigated, since it has been reported that upon irradiation of Fe(III)-EDDS the production of H2O2 can occur. SBP did not boost the 4-CP degradation, suggesting that the possibly produced H2O2 reacts immediately with the Fe(II) ion with a quick kinetics that does not allow the diffusion of H2O2 into the bulk of the solution (i.e., outside the solvent cage of the complex). So, a concerted mechanism in which the photochemically produced H2O2 and Fe(II) react inside the hydration sphere of the Fe(III)-EDDS complex is proposed.