Fenton Catalyst Research Articles

Amplified Cascade Catalysis for RAFT Polymerization.

We report a conceptually new amplified cascade catalysis that converts oxygen to hydroxyl radical for controlled RAFT polymerization. This catalysis consists of two sequential reactions, deoxygenation catalyzed by glucose oxidase and Fenton reaction catalyzed by ferrocene. The two catalysts can communicate with each other, leading to ferrocene recycling and hence amplification in radical generation. Ferrocene recycling was confirmed by UV-vis spectroscopy, molecular docking simulation, electron paramagnetic resonance spectroscopy, as well as polymerization studies. This catalysis was applied to RAFT polymerization of various monomers, yielding well-defined homopolymers and diblock copolymers with controlled molecular weights and low dispersities. Poly(N,N-dimethyl acrylamide) with molecular weight over 1 million g mol-1 was also successfully synthesized under ambient conditions. Ferrocene-functionalized microspheres were prepared and used as recyclable Fenton catalyst for five consecutive polymerizations with minimal declination in monomer conversion, which further improved the ecofriendly character of this polymerization methodology.

Proton nanomodulators for enhanced Mn2+-mediated chemodynamic therapy of tumors via HCO3− regulation

BackgroundMn2+-mediated chemodynamic therapy (CDT) has been emerged as a promising cancer therapeutic modality that relies heavily on HCO3− level in the system. Although the physiological buffers (H2CO3/HCO3−) provide certain amounts of HCO3−, the acidity of the tumor microenvironment (TME) would seriously affect the HCO3− ionic equilibrium (H2CO3 ⇌ H+ + HCO3−). As a result, HCO3− level in the tumor region is actually insufficient to support effective Mn2+-mediated CDT.ResultsIn this study, a robust nanomodulator MnFe2O4@ZIF-8 (PrSMZ) with the capability of in situ self-regulation HCO3− is presented to enhance therapeutic efficacy of Mn2+-mediated CDT. Under an acidic tumor microenvironment, PrSMZ could act as a proton sponge to shift the HCO3− ionic equilibrium to the positive direction, significantly boosting the generation of the HCO3−. Most importantly, such HCO3− supply capacity of PrSMZ could be finely modulated by its ZIF-8 shell thickness, resulting in a 1000-fold increase in reactive oxygen species (ROS) generation. Enhanced ROS-dependent CDT efficacy is further amplified by a glutathione (GSH)-depletion ability and the photothermal effect inherited from the inner core MnFe2O4 of PrSMZ to exert the remarkable antitumor effect on mouse models.ConclusionsThis work addresses the challenge of insufficient HCO3− in the TME for Mn2+-mediated Fenton catalysts and could provide a promising strategy for designing high-performance Mn2+-mediated CDT agents to treat cancer effectively.

MgCo2O4@g‐C3N4 Composite Induced Peroxymonosulfate Activation for Effective Degradation of Tetracycline Under Visible Light

AbstractThe composite Fenton catalyst was prepared by attaching MgCo2O4 to the surface of g‐C3N4 using a one‐pot method after preparing MgCo2O4 through co‐precipitation. The microstructure of the composites was analyzed using X‐ray diffraction (XRD) and other characterization methods. The catalytic activity of the composites towards tetracycline (TC) was studied, and a possible catalytic mechanism was proposed. The experimental results indicate that the degradation of TC by MgCo2O4@g‐C3N4 reached almost 99.0 % within 30 min in the presence of PMS and visible light. The combination of MgCo2O4 and g‐C3N4 improved the absorption of visible light, and the energy level‐matched heterojunction facilitated the separation of photogenerated electrons and holes, accelerating the redox cycle of ≡Co3+/≡Co2+. The free radical quenching experiment confirmed that the main active substances were free radical ⋅O2− and 1O2. The one‐step synthesis of composite catalysts exhibits high catalytic performance and good stability, offering a potential solution for the efficient treatment of tetracycline wastewater.

Highly improved degradation of benzohydroxamic acid by bubble-propelled heterogeneous Fenton catalysts of halloysite/MnFe2O4: Enhancing mass transfer and accelerating Fe/Mn cycle

This work focuses on the effective degradation of benzohydroxamic acid (BHA) using a novel bubble-propelled heterogeneous Fenton catalyst of halloysite/MnFe2O4 (HM). The results demonstrate that almost 90 % of BHA at a concentration of 10 mg/L could be degraded by 15 %-HM catalysts in 1 h. Additionally, 15 %-HM catalysts exhibited promising performance under complex environmental conditions. The enhanced catalytic ability of 15 %-HM catalysts may be attributed to improved mass transfer and accelerated Fe/Mn redox cycling. 15 %-HM can be propelled at an average speed of 126 μm/s by a low H2O2 concentration of 0.5 %, resulting in a 4.3-fold increase in mass transfer efficiency. The degradation of BHA was primarily by ·OH, while ·O2- mediated the electron transfer between Fe and Mn species. This work presents a novel idea for the preparation of bubble-propelled heterogeneous Fenton catalysts and offers insights into the high-efficient degradation mechanism of BHA.

Removal of Methylene Blue from Aqueous Solution through Adsorption and Heterogeneous Fenton Reaction using Iron Oxides Produced by Different Methods

Direct discharge of industrial wastewater containing dyes into water bodies has contributed to the scarcity of drinking water. As environmental legislation becomes stricter, it is increasingly important to develop efficient methods for wastewater treatment. Traditional methods are commonly costly and have limited efficiency. This study aimed to prepare iron oxides via different synthetic routes and evaluate the effect of synthesis method on the efficiency of these materials as adsorbents and heterogeneous Fenton catalysts for the removal of methylene blue from aqueous solution. Iron oxides were synthesized by non-hydrolytic sol–gel (NHSG) and co-precipitation (CP) methods, followed by hydrothermal treatment for different times. CP oxides demonstrated high efficiency in dye adsorption, particularly the sample subjected to hydrothermal treatment for 6 h (CP-R6). This sample achieved 94.04% removal in 120 min. NHSG materials, by contrast, were less effective. The CP series of materials showed superior catalytic performance in heterogeneous Fenton experiments, with CP-R6 reaching 98.79% decolorization in 240 min. X-ray diffraction analysis indicated that iron oxides were composed of crystalline hematite and maghemite. Scanning electron microscopy revealed that CP materials were more porous and homogeneous than NHSG materials. The results demonstrated the efficiency of the developed iron oxides in removing methylene blue via adsorption and heterogeneous Fenton degradation and clarified how synthesis method influences adsorptive and catalytic properties.

Enhanced dye degradation using MIL-53(Fe)-Modified kraft lignin as a heterogeneous Fenton catalyst

MIL-53(Fe), a metal–organic framework (MOF), is capable of degrading harmful organic contaminants, but it has relatively low Fenton catalytic efficiency. To enhance the degradation performance of MIL-53(Fe), we synthesized MIL-53(Fe)-MKL by incorporating modified kraft lignin (MKL) into pristine MIL-53(Fe). The as-prepared composite demonstrated Fenton activity, degrading 97 % of methylene blue (MB) within 50 min. Compared to pristine MIL-53(Fe) (which achieved 62.4 % MB degradation), the MIL-53(Fe)-MKL composite showed a 34.6 % improvement in MB degradation under identical reaction conditions. The incorporated MKL promotes Fe2+ regeneration from Fe3+ in the Fenton process, activating H2O2 to produce OH radicals, which were identified through scavenging experiments and chemical dosimetry with ESR analysis. The MIL-53(Fe)-MKL composite was reused for at least five cycles without a significant decrease in catalytic efficiency. This reported catalyst takes advantage of both MKL and MIL-53(Fe) to enhance catalytic activity, providing a basis for developing innovative catalysts for organic pollutant degradation.

Repurposing waste-iron electrocoagulated algal biomass as effective heterogenous (bio)electro-fenton catalyst for phthalate removal from wastewater

The presence of refractory micropollutants in natural waters poses significant environmental and health risks. Preferably, advanced oxidation techniques like electro-Fenton (EF) and bio-electro-Fenton (BEF) are used to mitigate micropollutants; nevertheless, their field-scale implementation is limited by prohibitive catalyst cost. As an alternative, waste-iron electrocoagulated algal biomass (A-BC/Fe) was explored as a heterogeneous Fenton catalyst to eliminate dimethyl phthalate (DMP) from wastewater. The Fenton-conducive morphological, chemical, and electrochemical properties of the A-BC/Fe catalyst were revealed by detailed characterisation. In EF treatment, 10 mg/L of DMP was completely degraded within 15 min at pH of 7.0, 50 mM Na2SO4, and cathode potential of − 1.4 V vs. Ag/AgCl. Moreover, the EF system achieved 87.80 ± 2.10% and 96.14 ± 1.10% of DMP removal from secondary and tertiary treated municipal sewage, respectively. The A-BC/Fe catalyst-driven EF process disintegrated DMP into benign non-toxic by-products and showed stable performance over eight batch cycles with only a 1.71% decline in DMP removal efficiency. Further, the A-BC/Fe-catalysed BEF system eliminated 94.81 ± 1.90% of DMP in 4 h while achieving a maximum power density of 124.03 ± 5.64 mW/m2. This investigation underscores the potential of repurposing electrocoagulated algal biomass as a sustainable heterogenous catalyst for micropollutant remediation.

Ball milling of pyrite in air to significantly promote the Fenton reaction: A mechanistic study

Natural pyrite (FeS2) has been widely used as heterogenous Fenton catalyst due to the unique iron supplying and ferrous regeneration performance, however, natural pyrite has poor catalytic activity due to the low surface reactivity. Ball milling is commonly used to modify pyrite, but the mechanism has not been thoroughly studied. In our work, by optimizing the ball milling conditions, the catalytic efficiency of modified pyrite is increased by 60 times compared to natural pyrite, and the ball milled pyrite Fenton system was able to degrade dyes and a series of antibiotics within 30 min. Compared to ball milling in nitrogen and vacuum, ball milling in air increased the proportion of S2− and active iron sites on the surface of pyrite, which assisted and accelerated the regeneration of ferrous and enhanced the iron supplying performance. This work explored the mechanisms of ball milling to modify the properties of pyrite, reported a green and efficient ball milled pyrite Fenton system, and provided a new insight in regulating ball milling conditions for mechanochemical modification.

Treatment of textile dyes with steel flakes via Fenton and Electro-Fenton processes: An experimental analysis

The textile production process is well recognised as one of the most water-intensive industries, with an estimated daily water consumption of several thousand cubic metres. The main objective of the study is to remove the colour and COD of three reactive dyes namely reactive blue, reactive yellow and reactive black by Fenton and Electro Fenton Process. In this research paper, new novel catalyst steel flakes have been employed as part of the Fenton and Electro-Fenton process, replacing the conventional Fenton and Electro-Fenton catalyst. Scanning Electron Microscope (SEM), Energy-Dispersive X-ray Analysis (EDAX), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Thermo Gravimetric Analysis (TGA) was done to characterize the steel flakes. The pH, dye concentration, FeSO4 dosage and H2O2 dosage were studied. The maximum colour and Chemical Oxygen Demand (COD) removal in Fenton process was 98.47 % and 74 % respectively. In Electro Fenton Oxidation the maximum colour and COD removal was 99.65 % and 78 % respectively. The best colour and COD removal was observed by Fenton and Electro Fenton oxidation with optimum Fenton molar ratio of 50:1 and pH 3 in all three dyes. In the laboratory-scale feasibility tests on the Electro-Fenton process, the highest colour removal effectiveness was observed at catalyst dosages of 1 g/L, 132 mM H2O2, and pH 3. The novel modified heterogeneous Electro-Fenton approach presents a distinct cost-effectiveness benefit in comparison to both the conventional Electro-Fenton reaction and the Electro-Fenton reaction employing alternative iron sources.

A tartaric acid (TA)-coated iron-based biochar as heterogeneous fenton catalyst for enhanced degradation of dibutyl phthalate

Iron-biochar composite is a promising catalyst in Fenton-like system for removal of organic pollutants. Nevertheless, low cycling rate of Fe(III)/Fe(II), high iron leaching and low H2O2 utilization efficiency impedes its application. Herein, a iron-based biochar (C-Fe) coated with tartaric acid (TA) was synthesized. The specific structure of inherent graphitized carbon and TA coating improved the removal efficiency of dibutyl phthalate (DBP) to 93%, promoted 2-fold increase in HO• production in H2O2 activation, improved the cycling rate of Fe(III)/Fe(II), and mitigated Fe leaching significantly. The developed HO• and 1O2 dominated Fenton-like system had an excellent pH universality and anti-interference to inorganic ions and real water matrixes. Moreover, C-Fe-TA has been shown to efficiently degrade DBP by using the dissolved oxygen in water to generate HO•. This work provided a novel insight for sustainable and efficient HO• and 1O2 generation, which motivated the development of new water treatment technology based on efficient iron-biochar catalyst.

A Zwitterionic Hydrogel-Based Heterogeneous Fenton Catalyst for Water Treatment.

Persistent organic pollutants (POPs), including xenoestrogens and polyfluoroalkyl substances (PFAS), demand urgent global intervention. Fenton oxidation, catalyzed by iron ions, offers a cost-effective means to degrade POPs. However, numerous challenges like acid dependency, catalyst loss, and toxic waste generation hinder practical application. Efforts to create long-lasting heterogeneous Fenton catalysts, capable of simultaneously eliminating acid requirements, sustaining rapid kinetics, and retaining iron efficiently, have been unsuccessful. This study introduces an innovative heterogeneous zwitterionic hydrogel-based Fenton catalyst, surmounting these challenges in a cost-effective and scalable manner. The hydrogel, hosting individually complexed iron ions in a porous scaffold, exhibits substantial effective surface area and kinetics akin to homogeneous Fenton reactions. Complexed ions within the hydrogel can initiate Fenton degradation at neutral pH, eliminating acid additions. Simultaneously, the zwitterionic hydrogel scaffold, chosen for its resistance to Fenton oxidation, forms strong bonds with iron ions, enabling prolonged reuse. Diverging from existing designs, the catalyst proves compatible with UV-Fenton processes and achieves rapid self-regeneration during operation, offering a promising solution for the efficient and scalable degradation of POPs. The study underscores the efficacy of the approach by demonstrating the swift degradation of three significant contaminants-xenoestrogens, pesticides, and PFAS-across multiple cycles at traceconcentrations.

Construction of heterojunction superparamagnetic Cd0.5Ag0.5Fe2O4 nanocomposite photocatalyst for simulated textile effluent oxidation

Abstract Significant attempts have been recently made regarding nanomaterials due to their several environmental applications especially in wastewater treatment technologies. Among the available nanoparticles, ferrite based substances are gaining a special interest since their superior characteristics such as their magnetic nature, high adsorption capacity and large specific surface area. In this regard, Cd0.5Ag0.5Fe2O4 was prepared using the green simple co-precipitation route. Then, the sample is characterized via Scanning Electron Microscopy (SEM) that proved the produced material’s surface morphology. The substance is then employed as a catalyst source for Fenton reaction to oxidize textile effluent solution containing Rhodamine B (Rh-B 6G) dye. The oxidation experiment conducted under ultraviolet (UV) light with the ferrite-based Fenton catalyst supplemented with hydrogen peroxide showed an exceptional removal rate of up to 94% removals. Notably, the oxidation system is significantly impacted by the operational variables. The oxidation efficiency of the dye was maximized at pH 3.0 and 50 mg/L and 1600 mg/L for ferrite-based Fenton catalyst and H2O2, respectively. The impacts of the operational factors, i.e. initial pH value, initial dye concentration, catalyst, and H2O2 concentrations were also investigated. This perspective introduces the role of a superparamagnetic material to be a recyclable sustained catalyst.

Manganese oxide for heterogeneous Fenton treatment: Catalyst or inhibitor?

Manganese oxide species have been frequently used for Fenton catalyst design, but their role in reaction with hydrogen peroxide (H2O2) is still in debate. We here revealed the different routes of manganese oxide/H2O2 interactions occurring at bulk surfaces to that at nanopore-confined surfaces, which have been overlooked in literatures. Briefly, particulate manganese oxide species cause a fast H2O2 decomposition influenced by the valence of manganese and solution pH, but without generation of reactive oxygen species (•OH, •O2-, or 1O2) for water treatment; in contrast, manganese oxide/H2O2 interaction under nanopore confinement (ca. 1 nm) led to the production of radicals (mainly •OH and •O2-) and the removal of organic pollutants. We gained insights into the differed reaction routes based on experimental and computational study. Our findings provide caveats on the indiscriminate pursuit of manganese in Fenton catalyst development, against a nullified H2O2 decomposition and impractically slow radical production.

Design and characterisation of activated magnetic zeolite 4A from naturally occurring kaolin clay of Cameroonian origin for optimised dye removal by Fenton-like degradation

ABSTRACT The transformation of local clay material of Cameroonian origin into magnetic zeolite (Fe@Zeo-4A) for the degradation of acid-blue 90 in solution was investigate herein. The insertion of magnetic iron oxide particles into the zeolitic framework of Zeo-4A was achieved via hydrothermal synthesis. FT-IR spectroscopy, XRD and SEM confirmed the transformation of the clay into zeolite while EDX analysis and elemental mappings confirmed the presence of iron in the magnetic zeolite. Fe@Zeo-4A was strongly attracted to an external magnetic field. N2 adsorption-desorption studies revealed a considerable decrease in specific surface area and pore volume from the zeolite to the magnetic zeolite, suggesting the occupation of the pores of the zeolite by magnetite. The central composite design of the response surface methodology was used as optimisation approach for four parameters affecting the efficiency of degradation: solution pH, H2O2 concentration, initial dye concentration and time of stirring. ANOVA results revealed good correlation between the experimental and predicted results as well as the suitability of the linear regression model for describing the dye degradation process. An adjusted correlation coefficient of 85.17% was obtained for the dye degradation model. An optimal degradation percentage of 95.2% was obtained experimentally under optimal conditions of 7.6 for pH, 20 mg/L for dye concentration, 15.0 mol/L for [H2O2] and 15 min for time, in close agreement with a theoretical response of 96.6% predicted by the model. The magnetic zeolite was found to exhibit good stability over a wide pH range and lost only about 18% of its catalytic efficiency after five cycles of degradation experiments. Therefore, the novel magnetic zeolite-based material is an efficient Fenton catalyst for treating dye-contaminated wastewater.

Simultaneous Solar‐Driven Interfacial Evaporation and Photo‐Fenton Oxidation by Semiconducting Metal–Organic Framework From Waste Polyimide

The integrated technology of interfacial solar steam generation and photo‐Fenton oxidation has emerged as a promising way to simultaneously mitigate freshwater scarcity and degrade organic pollutants. However, fabricating low‐cost, multi‐functional evaporators with high water evaporation and catalytic ability still presents a significant challenge. Herein, we report the functional upcycling of waste polyimide into semiconducting Fe‐BTEC and subsequently construct Fe‐BTEC‐based composite evaporators for simultaneous freshwater production and photo‐Fenton degradation of pollutants. Firstly, through a two‐step solvothermal‐solution stirring method, Fe‐BTEC nanoparticles with the size of 20–100 nm are massively produced from waste polyimide, with a band gap energy of 2.2 eV. The composite evaporator based on Fe‐BTEC and graphene possesses wide solar‐spectrum absorption capacity, high photothermal conversion capacity, rapid delivery of water, and low enthalpy of evaporation. Benefiting from the merits above, the composite evaporator achieves a high evaporation rate of 2.72 kg m−2 h−1 from tetracycline solution, as well as the photothermal conversion efficiency of 97% when exposed to irradiation of 1 Sun, superior to many evaporators. What is more, the evaporator exhibits the tetracycline degradation rate of 99.6% with good recycling stability, ranking as one of the most powerful heterogeneous Fenton catalysts. COMSOL Multiphysics and density functional theory calculation results prove the synergistic effect of the concentrated heat produced by interfacial solar steam generation and catalytic active sites of Fe‐BTEC on promoting H2O2 activation to form reactive oxidation radicals. This work not only provides a green strategy for upcycling waste polyimide, but also proposes a new approach to fabricate multi‐functional evaporators.

Synthesis of iron loaded jackfruit peel biochar through microwave heating as a stable and active heterogenous Fenton catalyst for dye degradation

Iron-loaded biochar derived from jackfruit peels (Fe-JP) was synthesised by pyrolysis in a microwave furnace and iron was loaded onto the peels prior to pyrolysis, facilitated by sonication. The primary objective of the investigation was to examine the degradation process of methylene blue (MB) dye and Acid Red 1 (AR1) dye by the using Fe-JP biochar as a heterogeneous Fenton catalyst. The investigation encompassed an examination of the impact of different operating parameters, such as pH, catalyst dosage, and H2O2 concentration. The synthesised Fenton catalyst underwent characterization using Field Emission scanning electron microscopy (FESEM), Energy Dispersive X-ray (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) techniques, Fourier transform infrared (FTIR) spectra analysis, Raman spectroscopy, Brunauer-Emmet-Teller (BET) analysis. At a pH of 3, using an initial MB dye concentration of 20 mg/L and initial AR1 dye concentration of 50 mg/L, an 8 mM H2O2 concentration, and a catalyst dose of 2 g/L, the maximum dye removal efficiency reached 96.5 % and 98 % respectively, while the total organic carbon (TOC) removal efficiency reached 68.5 % and 75 % respectively. The observed reaction time under the given experimental conditions was 120 min. The thermal stability of the biochar catalyst was found to be excellent based on the Thermogravimetric analysis (TGA) and Differential Scanning Calorimeter (DSC) studies. The catalysts that were developed demonstrated remarkable durability and negligible leaching of iron, hence enabling their repeated usage in subsequent cycles. The findings of the investigation suggest that the primary mechanism responsible for the degradation of the dye was the surface-based heterogeneous Fenton activity. Additionally, the effect of adsorption on the elimination of colour under varying pH conditions was examined, which had a very low influence in dye degradation (<30 %). The conducted scavenging investigations in the research have indicated the major involvement of hydroxyl radicals (OH) in the degradation process, followed by surface-bound hydroxyl radicals (OHsurface), superoxide radicals (O2−) and ultimately by singlet oxygen radicals (1O2). The study's economic analysis demonstrated that using microwave mode of heating for catalyst synthesis is both green and cost-effective. This observation suggests the possibility of practical implications in the domain of dye degradation.

Pd octahedra nanocubes mediated photo-fenton catalytic performance for sustainable degradation of methylene blue

This research utilized a typical solvothermal approach, by employing Na2PdCl4 as the synthetic precursor, L-ascorbic acid (AA) as the reductant agent, and polyvinylpyrrolidone (PVP) as the practical surfactant, palladium (Pd) octahedra was finally effectively synthesized by the hydrothermal and solvothermal methods. Subsequently, characterizations of Pd octahedra were conducted by using TEM, XPS, XRD, and other analytical methods. Whereafter, Pd octahedra displayed a consistent shape and size, featuring a distinctive tip-shaped structure, which conferred upon them outstanding optical absorption properties within the near-infrared (NIR) region. Consequently, under NIR laser exposure, Pd octahedra could elevate local reaction temperature via in-situ photothermal conversion, thereby stimulating the formation of active sites of Fenton catalysts. The Photo-Fenton catalytic activity of Pd octahedra was investigated by using methylene blue (MB) as a model pollutant. The degradation efficiency of MB reached 94.8 % within 35 min under 808 nm laser irradiation, and the removal rate of MB by Pd octahedra could still reach more than 90 % after five cycles of use. All the results manifest that Pd octahedra exhibit excellent purification performance for MB dyestuff wastewater.

SIDOARJO VOLCANIC MUD AS PROMISING FENTON CATALYST FOR REMOVAL OF CONGO RED DYE

Sidoarjo mud is a volcanic mud (VM) that continues erupting in Sidoarjo to this day. The VM has the potential to be used in water treatment technology as a reagent or catalyst due to enormous amount of discharged flow and rich mineral content. Heterogeneous Fenton is one promising process for maximizing the VM potential, however customization is essential to optimize the process. Aim: This study aimed to investigate the catalytic abilities of Sidoarjo VM in Fenton oxidation by several modification approaches, such as calcination (CVM), impregnation-calcination (ICVM), and unmodified (UVM). Methodology and results: Fenton oxidation was carried out in a batch reactor system with the following conditions: initial congo red (CR) concentration= 50 mg/L; VCR=300mL pH=2; agitation speed=300 rpm; catalyst dosage=0.5 g/L; dan H2O2 concentration=485 mg/L. The highest performance results were achieved when the process was combined with adsorption, at 90% (CVM), 55% (ICVM), and 52% (UVM), respectively. Conclusion, significance, and impact study: The Sidoarjo volcanic mud shows high potential as a Fenton catalyst in the UVM modification technique with CVM reveals to be more suitable as an adsorbent.

Heterogeneous activation of self-generated H2O2 by Pd@UiO-66(Zr) for trimethoprim degradation: Efficiency and mechanism

The Fenton reaction is recognized as an effective technique for degrading persistent organic pollutants, such as the emerging pollutant trimethoprim (TMP). Recently, due to the excellent reducibility of active hydrogen ([H]), Pd–H2 has been preferred for Fenton-like reactions and the specific H2 activation of Pd-based catalysts. Herein, a heterogeneous Fenton catalyst named the hydrogen-accelerated oxygen reduction Fenton (MHORF@UiO-66(Zr)) system was prepared through the strategy of building ships in the bottle. The [H] has been used for the acceleration of the reduction of Fe(III) and self-generate H2O2. The systematic characterization demonstrated that the nano Pd0 particle was highly dispersed into the UiO-66(Zr). The results found that 20 mg L−1 of TMP was thoroughly degraded within 90 min in the MHORF@UiO-66(Zr) system under conditions of initial pH 3, 30 mL min−1 H2, 2 g L−1 Pd@UiO-66(Zr) and 25 μM Fe2+. The hydroxyl radical as well as the singlet oxygen were evidenced to be the main reactive oxygen species by scavenging experiments and electron spin resonance. In addition, both reducing Fe(III) and self-generating H2O2 could be achieved due to the strong metal-support interaction (SMSI) between the nano Pd0 particles and UiO-66(Zr) confirmed by the correlation results of XPS and calculation of density functional theory. Finally, the working mechanism of the MHORF@UiO-66(Zr) system and the possible degradation pathway of the TMP have been proposed. The novel system exhibited excellent reusability and stability after six cyclic reaction processes.

Performance and Mechanism of the Modified Group Regulated the MIL-101(Fe) Type Fenton-like Catalysts.

In order to avoid the disadvantages of the Fenton process in wastewater treatment and reduce the cost of wastewater treatment, a series of MIL-101(Fe)-X (X = -OH, -NH2, -NO2, -H) solid Fenton catalysts were successfully prepared. The performance of these Fenton-like catalysts was studied with the Fenton experiment as a reference and methylene blue (MB) as an organic pollutant. The effects of the H2O2 concentration, catalyst dosage, and reaction pH on catalytic performance were systematically studied. The research had shown that the optimal concentration of H2O2 for catalytic reactions was 0.10 mmol/L and the pH was 3. At this point, their catalytic degradation MB performance was superior to the Fenton reaction and photocatalytic reaction. When the H2O2 participated in the reaction, the performance of MIL-101(Fe)-X (X = -OH, -NH2, -NO2, -H) in catalyzing the degradation of MB followed the rule of -OH > -NH2 > -NO2 > -H. This was due to the synergistic effect of Fenton-like catalysis and photocatalytic degradation in the catalytic degradation of MB. In addition, the electron paramagnetic resonance and electrospray ionization mass spectrometry showed that the hydroxyl radical (·OH) generated during the catalytic process first underwent a redox reaction with the highly electronegative functional groups in the MB molecule, and finally oxidized it to CO2 and H2O. This study successfully prepared commercially applicable Fenton-like catalysts and explored their optimal reaction conditions. This provides a technical reference for wastewater treatment.