Fenton-like Reagent Research Articles

Rapid and Highly Selective Fe(IV) Generation by Fe(II)-Peroxyacid Advanced Oxidation Processes: Mechanistic Investigation via Kinetics and Density Functional Theory.

High-valent iron (Fe(IV/V/VI)) has been widely applied in water decontamination. However, common Fe(II)-activating oxidants including hydrogen peroxide (H2O2) and persulfate react slowly with Fe(II) and exhibit low selectivity for Fe(IV) production due to the cogeneration of radicals. Herein, we report peroxyacids (POAs; R-C(O)OOH) that can react with Fe(II) more than 3 orders of magnitude faster than H2O2, with high selectivity for Fe(IV) generation. Rapid degradation of bisphenol A (BPA, an endocrine disruptor) was achieved by the combination of Fe(II) with performic acid (PFA), peracetic acid (PAA), or perpropionic acid (PPA) within one second. Experiments with phenyl methyl sulfoxide (PMSO) and tert-butyl alcohol (TBA) revealed Fe(IV) as the major reactive species in all three Fe(II)-POA systems, with a minor contribution of radicals (i.e., •OH and R-C(O)O•). To understand the exceptionally high reactivity of POAs, a detailed computational comparison among the Fenton-like reactions with step-by-step thermodynamic evaluation was conducted. The high reactivity is attributed to the lower energy barriers for O-O bond cleavage, which is determined as the rate-limiting step for the Fenton-like reactions, and the thermodynamically favorable bidentate binding pathway of POA with iron. Overall, this study advances knowledge on POAs as novel Fenton-like reagents and sheds light on computational chemistry for these systems.

Enhanced humification attributed by the integration of Fenton reagent and oxalic acid during a co-composting of swine manure and corn straw: Impacts and the possible mechanisms

To illustrate the role and mechanism of using oxalic acid (OA) and Fenton reagent to enhance carbon transformation and humification in the co-composting of swine manure and corn straw, four different treatments, SW1 (Control), SW2 (Fenton reagent), SW3 (10 % OA), and SW4 (Fenton reagent + 10 % OA) were set up for an 80-day pilot-scale composting. Compared with the Fenton pretreatment, the contents of Fe (II) and hydroxyl radicals (·OH) in the SW4 treatment increased by 20.25 %-54.55 % and 6.39 %-71.00 %, respectively. This confirmed the role of OA in protecting Fe (II) and maintaining the generation of ·OH during the composting. Compared with Control, Fenton-like reagent amendment facilitated decomposition of dissolved organic carbon and total organic matter by 20.53 % and 25.37 %, respectively, which led to a higher content of humic substances (141.81 mg/g) and a higher degree of polymerization (3.51) in SW4. Among all, the dissolved organic carbon in the compost substrate of SW4 treatment showed the highest level of aromatization and more refractory organic matter decomposition. The compact microbial co-occurrence network analysis exhibited the high-metabolic activity in Fenton-like treatment (SW4). Therefore, the probable mechanism of humification facilitation by Fenton-like reagent amendment in co-composting could be controlled by several processes: 1) generation of ·OH for facilitating the decomposition of organic matter, 2) disintegration of refractory lignocellulose substances by promoting the lignin pathway of humification, and 3) increasing the quantity and activity of microbes (i.e., Proteobacteria, Actinobacteriota, Chloroflexi, Ascomycota and Basidiomycota) involved in humification. This study provided a profound understanding of Fenton-like reagent amendments in co-composting of agricultural solid wastes and proposes a solution for enhancing the humification degree of compost products for agricultural use.

Different Valence States of Copper Ion Delivery against Triple-Negative Breast Cancer.

Different valence states of copper (Cu) ions are involved in complicated redox reactions in vivo, which are closely related to tumor proliferation and death pathways, such as cuproptosis and chemodynamic therapy (CDT). Cu ion mediated Fenton-like reagents induced tumor cell death which presents compelling attention for the CDT of tumors. However, the superiority of different valence states of Cu ions in the antitumor effect is unknown. In this study, we investigated different valence states of Cu ions in modulating tumor cell death by Cu-chelated cyanine dye against triple-negative breast cancer. The cuprous ion (Cu+) and copper ion (Cu2+) were chelated with four nitrogen atoms of dipicolylethylenediamine-modified cyanine for the construction of Cu+ and Cu2+ chelated cyanine dyes (denoted as CC1 and CC2, respectively). Upon 660 nm laser irradiation, the CC1 or CC2 can generate reactive oxygen species, which could disrupt the cyanine structure, achieving the rapid release of Cu ions and initiating the Fenton-like reaction for CDT. Compared with Cu2+-based Fenton-like reagent, the CC1 with Cu+ exhibited a better therapeutic outcome for the tumor due to there being no need for a reduction by glutathione and a shorter route to generate more hydroxyl radicals. Our findings suggest the precision delivery of Cu+ could achieve highly efficient antitumor therapy.

Metallic Copper-Based Dual-Enzyme Biomimetic Nanoplatform for Mild Photothermal Enhancement of Anticancer Catalytic Activity.

Background: Chemodynamic therapy (CDT) is recognized as a promising cancer treatment. Recently, copper sulfide nanostructures have been extensively employed as Fenton-like reagents that catalyze the formation of acutely toxic hydroxyl radicals (·OH) from hydrogen peroxide (H2O2). However, CDT therapeutic potency is restricted by the tumor microenvironment (TME), such as insufficient amounts of hydrogen peroxide, excessive glutathione levels, etc. To address these disadvantages, glucose oxidase (GOx) or catalase (CAT) can be utilized to enhance CDT, while low therapeutic efficacy still inhibits their future applications. Our previous study revealed that mild photothermal effect could boost the CDT catalytic effectiveness as well as GOx enzyme activity over a range. Results: We engineered and constructed a hollow CuS nanoplatform loaded with GOx and CAT, coating with macrophage membranes (M@GOx-CAT@CuS NPs). The nanoplatforms allowed enhancement of the reactive oxygen species creation rate and GOx catalytic activeness of CDT through mild phototherapy directed by photoacoustic imaging. After actively targeting vascular cell adhesion molecule-1 (VCAM-1) in cancer cells mediated by macrophage membrane coating, M@GOx-CAT@CuS NPs released GOx and CAT under near-infrared irradiation. GOx catalyzed the formation of H2O2 and gluconic acid with glucose, creating a better catalytic environment for CDT. Meanwhile, CAT-catalyzed H2O2 decomposition to generate sufficient oxygen, appropriately alleviating the oxygen shortage in the TME. In addition, starvation effects decreased adenosine triphosphate levels and further underregulated heat shock protein expression to reduce the heat resistance of tumor cells, resulting in a better mild phototherapy outcome. Both invitro and invivo experiments demonstrated that the newly developed M@GOx-CAT@CuS nanoplatform has remarkable synergistic anticancer therapeutic effects. Conclusion: The cascade reaction-enhanced biomimetic nanoplatform opens up a new avenue for precision tumor diagnostic and therapeutic research.

A self-assembled copper-artemisinin nanoprodrug as an efficient reactive oxygen species amplified cascade system for cancer treatment.

Chemodynamic therapy (CDT) is a tumor-specific intervention methodology, which is based on the upregulation of reactive oxygen species (ROS) content by triggering the Fenton or Fenton-like reaction within the tumor microenvironment (TME). However, there are still challenges in achieving high-efficiency CDT on account of both the limited intracellular hydrogen peroxide (H2O2) and delivery efficiency of Fenton metal ions. Copper-based nanotherapeutic systems have attracted extensive attention and have been widely applied in the construction of nanotherapeutic systems and multimodal synergistic therapy. Herein, we propose a strategy to synergize chemotherapy drugs that upregulate intracellular ROS content with chemodynamic therapy and construct an artemisinin-copper nanoprodrug for proof-of-concept. With the proposed biomimetic self-assembly strategy, we successfully construct an injectable nanoprodrug with suitable size distribution and high drug loading content (68.1 wt%) through the self-assembly of amphiphilic artemisinin prodrug and copper ions. After reaching the TME, both Cu2+ ions and free AH drugs can be released from AHCu nanoprodrugs. Subsequently, the disassembled Cu2+ ions are converted into Cu+ ions by consuming the intracellular GSH. The generated Cu+ ions serve as a highly efficient Fenton-like reagent for robust ROS generation from both AH and tumor-over-produced H2O2. Results show that the nanoprodrug can realize the cascade amplification of ROS generation via artemisinin delivery and subsequent in situ Fenton-like reaction and a high tumor inhibition rate of 62.48% in vivo. This work provides a promising strategy for the design and development of an efficient nanoprodrug for tumor-specific treatment.

A Detailed Insight into the Effects of Morphologies of Cerium Oxide on Fenton-like Reactions for Different Applications.

As an exceptional Fenton-like reagent, cerium oxide (CeO2 ) finds applications in biomedical science and organic pollutants treatment. The Fenton-like reaction catalyzed by CeO2 typically encompasses two distinct processes: one resembling the classical Fenton reaction, wherein cerium (Ce3+ ) triggers the decomposition of hydrogen peroxide (H2 O2 ) to yield reactive oxygen species (ROS), and the other involves the complexation of H2 O2 on the Ce3+ surface, leading to the formation of peroxides. However, the influence of diverse CeO2 morphologies on these two reaction pathways has not been comprehensively explored. In this study, CeO2 exhibiting three typical morphologies, rods, cubes, and spheres, were prepared. The generation of ROS and peroxides was evaluated using the 3,3,5,5-tetramethylbenzidine (TMB) oxidation reaction and the reduction current of H2 O2 , respectively. Moreover, the impacts of pH variations and CeO2 /H2 O2 concentrations on the production and conversion of these two reaction products were investigated. To corroborate the distinctions between the resultant products and their applicability, apoptosis assays and acid orange 7 (AO7) degradation analyses were performed. Notably, CeO2 rods exhibited the highest proportion of Ce3+ , predominantly engaging in complexation with H2 O2 to foster peroxide formation, thereby facilitating the robust degradation of AO7. However, the generated peroxides appeared to occupy Ce3+ sites, thereby impeding the H2 O2 decomposition process. Conversely, Ce3+ species on the surface of CeO2 cubes were primarily involved in H2 O2 decomposition, leading to heightened ROS production, and thus showcasing substantial potential for damaging A549 tumor cells. It is worth noting that the ability of these Ce3+ species to form peroxides through complexation with H2 O2 was comparatively reduced. In summation, this study sheds light on the intricate interplay between distinct CeO2 morphologies and their divergent impacts on Fenton-like reactions. These findings expand our comprehension of the influences on its reactivity of CeO2 morphologies and open new insights for applications in diverse domains, from organic dye degradation to tumor therapy.

Study on Treatment Performance of Desulfurization Wastewater by Zero-Valent Iron Fenton-like Process

In this study, the zero-valent iron Fenton reagent (ZVI Fenton-like) system was combined with the chemical precipitation method for the deep treatment of desulfurization wastewater from coal-fired power plants, and the chemical oxygen demand (COD) was used as the evaluation criterion for organic matter in the desulfurization wastewater. The effects of reaction time, H2O2 dosage, zero-valent iron dosage, pH, and reaction temperature were also investigated. The results showed that the COD concentration of the effluent was the lowest when the running time of the ZVI Fenton-like reagent system was 1 h, the dosage of H2O2 was 33.3 mg·L−1, the dosage of iron was 0.075 g·L−1, the pH was 4.5~6.5, the reaction temperature was 35 °C, the COD concentration of the wastewater was the lowest and its operating conditions were the best, and the internal reaction mechanism was finally deduced. In summary, the zero-valent iron Fenton reagent system provides a new idea for the treatment of desulfurization wastewater from coal-fired power plants.

Synthesis of nanomagnetite/copper oxide/potassium carrageenan nanocomposite for the adsorption and Photo-Fenton degradation of Safranin-O: kinetic and thermodynamic studies

In the current study, a novel nanomaterial called nanomagnetite/copper oxide/potassium carrageenan nanocomposite (MKCO) was fabricated to include Fenton (nanomagnetite, NM) and Fenton-like reagent (copper oxide nanoparticles, NCO) in a matrix of potassium carrageenan biopolymer. The prepared solid materials were characterized by different physicochemical techniques, such as TGA, N2 adsorption/desorption, SEM, TEM, XRD, DRS, pHPZC, and FTIR. The prepared MKCO showed unique properties like higher specific surface area of 652.50 m2/g, pore radius of 1.19 nm, pHPZC equals 7.80, and the presence of different surface chemical functional groups. Under various application conditions, comparative experiments between Safranin-O dye (SO) adsorption and Photo-Fenton catalytic degradation were conducted. After 24 h, MKCO had a maximum adsorption capacity of 384.61 mg/g at 42 °C, while the Photo-Fenton oxidation process took only 10 min to totally decompose 93% of SO at 21 °C. Based on the higher values of correlation coefficients, Langmuir’s adsorption model is the best-fitted adsorption model for SO onto all the prepared solid materials. Studies on SO adsorption’s kinetics and thermodynamics show that it is physisorption and that it operates according to endothermic, spontaneous, and PFO model processes. While, PFO, endothermic, and non-spontaneous processes are satisfied by the catalytic decomposition of SO. After five application cycles, MKCO demonstrated good catalyst reusability with a 3.4% decrease in degrading efficiency. For lower contaminant concentrations and shorter application times, Photo-Fenton catalytic degradation of organic pollutants is more effective than adsorption.Graphical abstractFenton and Photo-Fenton degradation of Safranin-O

Copper-Coordinated Covalent Organic Framework Produced a Robust Fenton-Like Effect Inducing Immunogenic Cell Death of Tumors.

Increasing infiltration of CD8+ T cells can enhance the response rate to immune checkpoint blockade (ICB) therapies. In contrast, immunogenic cell death (ICD) induced by intracellular reactive oxygen species (ROS) is an effective strategy to increase CD8+ T cell infiltration. Cuproptosis is newly defined and reported by Tsvetkov etal. A Cu-coordinated covalent organic framework (COF) in which two valence states of copper ions are simultaneously loaded is prepared. On the one hand, Cu2+ undergoes a valence shift generating Cu+ which acts as an effective Fenton-like reagent to catalyze the production of · OH and 1 O2 from cellular overexpressed H2 O2 , causing DNA damage and lipid peroxidation (LPO), which directly produce cytotoxicity. On the other hand, residual Cu2+ can effectively deplete endogenous cellular glutathione (GSH), converting it into glutathione disulfide (GSSG), further increasing intracellular oxidative stress and reducing the scavenging of ROS, thus further enhancing the Fenton-like effect and bringing toxic effects on tumor cells. The synergy of these two functions achieves ICD, helping for transforming "cold tumor" into "hot tumor" and efficient anti-tumor effects eventually. This work provides new insights into coordinated COF and inspire the development of more versatile COF for biomedical applications.

Highly Penetrable Drug-Loaded Nanomotors for Photothermal-Enhanced Ferroptosis Treatment of Tumor.

A kind of drug-loaded nanomotors with deep penetration was developed to improve the therapeutic effect of ferroptosis on tumor. The nanomotors were constructed by co-loading hemin and ferrocene (Fc) on the surface of bowl-shaped polydopamine (PDA) nanoparticles. The near-infrared response of PDA makes the nanomotor have high tumor penetration capability. In vitro experiments show that the nanomotors can exhibit good biocompatibility, high light to heat conversion efficiency, and deep tumor permeability. It is worth noting that under the catalysis of H2O2 overexpressed in the tumor microenvironment, the Fenton-like reagents hemin and Fc loaded on the nanomotors can increase the concentration of toxic •OH. Furthermore, hemin can consume glutathione in tumor cells and trigger the up-regulation of heme oxygenase-1, which can efficiently decompose hemin to Fe2+, thus producing the Fenton reaction and causing a ferroptosis effect. Notably, thanks to the photothermal effect of PDA, it can enhance the generation of reactive oxygen species and thus intervene in the Fenton reaction process, thereby enhancing the ferroptosis effect photothermally. In vivo antitumor results show that the drug-loaded nanomotors with high penetrability showed an effective antitumor therapeutic effect.

Hydroxyl radical production by abiotic oxidation of pyrite under estuarine conditions: The effects of aging, seawater anions and illumination

Pyrite is widely distributed in estuarine sediments as an inexpensive natural Fenton-like reagent, however, the mechanism on the hydroxyl radical (HO·) production by pyrite under estuarine environmental conditions is still poorly understood. The batch experiments were performed to investigate the effects of estuarine conditions including aging (in air, in water), seawater anions (Cl−, Br− and HCO3−) and light on the HO· production by pyrite oxidation. The one-electron transfer dominated the process from O2 to HO· induced by oxidation of pyrite. The Fe (oxyhydr)oxide coatings on the surface of pyrite aged in air and water consumed hydrogen peroxide while mediating the electron transfer, and the combined effect of the two resulted in a suppression of HO· production in the early stage of aging and a promotion of HO· production in the later stage of aging. Corrosion of the surface oxide layers by aggressive anions was the main reason for the inhibition of HO· production by Cl− and Br−, and the generation of Cl· and Br· may also play a role in the scavenging of HO·. HCO3− increased the average rate of HO· production through surface-CO2 complexes formed by adsorption on the surface of pyrite. The significant enhancement of HO· production under light was attributed to the formation of photoelectrons induced by photochemical reactions on pyrite and its surface oxide layers. These findings provide new insights into the environmental chemical behavior of pyrite in the estuary and enrich the understanding of natural remediation of estuarine environments.

Preparation of 2D Polyaniline/MoO3- x Superlattice Nanosheets via Intercalation-Induced Morphological Transformation for Efficient Chemodynamic Therapy.

Organic intercalation of layered nanomaterials is an attractive strategy to fabricate organic/inorganic superlattices for a wide range of promising applications. However, the synthesis of 2D organic/inorganic superlattice nanosheets remains a big challenge. Herein, the preparation of 2D polyaniline/MoO3- x (PANI/MoO3- x ) superlattice nanosheets via intercalation-induced morphological transformation from MoO3 nanobelts, as efficient Fenton-like reagents for chemodynamic therapy (CDT), is reported. Micrometer-long MoO3 nanobelts are co-intercalated with Na+ /H2 O followed by the guest exchange with aniline monomer for insitu polymerization to obtain PANI/MoO3- x nanosheets. Intriguingly, the PANI intercalation can induce the morphological transformation from long MoO3 nanobelts to 2D PANI/MoO3- x nanosheets along with the partial reduction of Mo6+ to Mo5+ , and generation of rich oxygen vacancies. More importantly, thanks to the PANI intercalation-induced activation, the PANI/MoO3- x nanosheets exhibit excellent Fenton-like catalytic activity for generation of hydroxyl radical (·OH) by decomposing H2 O2 compared with the MoO3 nanobelts. It is speculated that the good conductivity of PANI can facilitate electron transport during the Fenton-like reaction, thereby enhancing the efficiency of CDT. Thus, the polyvinylpyrrolidone-modified PANI/MoO3- x nanosheets can function as Fenton-like reagents for highly efficient CDT to kill cancer cells and eradicate tumors.

Effect of Pharmaceutical Sludge Pre-Treatment with Fenton/Fenton-like Reagents on Toxicity and Anaerobic Digestion Efficiency.

Sewage sludge is successfully used in anaerobic digestion (AD). Although AD is a well-known, universal and widely recognized technology, there are factors that limit its widespread use, such as the presence of substances that are resistant to biodegradation, inhibit the fermentation process or are toxic to anaerobic microorganisms. Sewage sludge generated by the pharmaceutical sector is one such substance. Pharmaceutical sewage sludge (PSS) is characterized by high concentrations of biocides, including antibiotics and other compounds that have a negative effect on the anaerobic environment. The aim of the present research was to determine the feasibility of applying Advanced Oxidation Processes (AOP) harnessing Fenton's (Fe2+/H2O2) and Fenton-like (Fe3+/H2O2) reaction to PSS pre-treatment prior to AD. The method was analyzed in terms of its impact on limiting PSS toxicity and improving methane fermentation. The use of AOP led to a significant reduction of PSS toxicity from 53.3 ± 5.1% to 35.7 ± 3.2%, which had a direct impact on the taxonomic structure of anaerobic bacteria, and thus influenced biogas production efficiency and methane content. Correlations were found between PSS toxicity and the presence of Archaea and biogas yields in the Fe2+/H2O2 group. CH4 production ranged from 363.2 ± 11.9 cm3 CH4/g VS in the control PSS to approximately 450 cm3/g VS. This was 445.7 ± 21.6 cm3 CH4/g VS (1.5 g Fe2+/dm3 and 6.0 g H2O2/dm3) and 453.6 ± 22.4 cm3 CH4/g VS (2.0 g Fe2+/dm3 and 8.0 g H2O2/dm3). The differences between these variants were not statistically significant. Therefore, due to the economical use of chemical reagents, the optimal tested dose was 1.5 g Fe2+/6.0 g H2O2. The use of a Fenton-like reagent (Fe3+/H2O2) resulted in lower AD efficiency (max. 393.7 ± 12.1 cm3 CH4/g VS), and no strong linear relationships between the analyzed variables were found. It is, therefore, a more difficult method to estimate the final effects. Research has proven that AOP can be used to improve the efficiency of AD of PSS.

Preparation of hydrogen sulfide adsorbent derived from spent Fenton-like reagent modified biochar and its removal characteristics for hydrogen sulfide

Hydrogen sulfide has serious harm to human health and equipment safety. Spent Fenton-like reagent poses a challenge to the environment. In this article, a cost-effective adsorbent was prepared from rice straw biochar modified with spent Fenton-like reagent, and was used to remove gaseous hydrogen sulfide. Effects of several parameters and gas components on hydrogen sulfide adsorption, and hydrogen sulfide adsorption mechanism were studied. Results show that spent Fenton-like reagent modification promotes the rise of active sites on biochar surface, but results in the decline of adsorbent specific surface area. The optimum calcination temperature of adsorbent is 300 °C, and the maximum adsorption capacity for hydrogen sulfide is up to 1000.6 mg/g at 120 °C, which is far more than similar adsorbents. Presence of gas components such as sulfur dioxide, nitric oxide or water vapor inhibits the desulfurization performance of adsorbent to varying degrees. Copper oxide is confirmed to be the key active substance for hydrogen sulfide adsorption on adsorbent, and copper sulphide, cuprous sulfide and elemental sulfur are found to be the main products of hydrogen sulfide removal on adsorbent. The study provides new ideas for utilization of spent Fenton-like reagent and development of cost-effective hydrogen sulfide adsorbent.

Ferrocenylseleno-dopamine functionalized carbon dots for redox-gated imaging and drug delivery in cancer cells

Fluorescent carbon dots (CDs) have aroused great interest in the nanomedicine due to their excellent chemical stability and biological compatibility. However, carbon dots-based nanoplatform integrated with targeted cancer imaging and responsive drug delivery are still challenging. Herein, we synthesized strongly green-fluorescent, cancer-cell-targeted and cationic carbon dots (HP-CDs) via hydrothermal method, by using hyaluronic acid (HA) and polyetherimide together as the starting materials. The nanoprobe could be specifically internalized with cancer cells, due to the recognition of surface HA with highly-expressed CD44 receptor. Ferrocenylseleno-dopamine (FcDA) was particularly designed as new generation drug of Fenton-like reagents, assembled on the surface of HP-CDs to obtain CDs@FcDA nanoprobe. In CDs@FcDA nanoprobe, FcDA significantly quenched CDs fluorescence due to photo-induced electron transfer. Upon the cellular specific uptake, ferrocene moiety of the nanoprobe would be oxidized into ferrocenium cation by intracellular H2O2 in a typical Fenton-like reaction, which resulted in charge reversal and drug release from HP-CDs surface. The quenched nanoprobe fluorescence was thus recovered and achieved the cancer-cell-specific imaging. Meantime, the Fenton chemistry produced toxic •OH, leading to the cancer cell apoptosis. Importantly, the composites of CDs@FcDA exhibited lower IC50 value than that of free FcDA for HeLa cell lines, indicating greater therapeutic efficiency of the drug nanoplatform. Moreover, oxidized ferrocenium could react with endogenous glutathione (GSH) and be reversibly restored to the reduced ferrocene, which formed a Fenton-chemistry cycle regulated by H2O2 and GSH in cancer microenvironment. Therefore, the HA-functionalized CDs@FcDA nanoprobe proposed in this work represents an attractive tool for redox-gated imaging and cancer-cell-responsive drug delivery.

Accelerated Fe(III)/Fe(II) cycle couples with in-situ generated H2O2 boosting visible light-induced Fenton-like oxidation

Conventional Fenton process operated along with high economic cost due to the requirement of highly acidic pH and an enormous addition of H2O2. And the low conversion rate of Fe(III)/Fe(II) may lead to decline of oxidation performance during the process. Here, we constructed a visible light-induced heterogeneous Fenton-like process on a novel Fenton-like catalyst which consisted of immobilized Fe(III)-TiO2 microspheres as Fenton-like reagent and g-C3N4-porphyrin lamella as in-situ H2O2 donor. The immobilized Fe species showed good stability and reduced the loss of Fe during Fenton-like process. Meanwhile, taking advantage of interfacial charge transfer (IFCT) effect among Fe(III)-TiO2 microspheres, the transformation from Fe(III) to Fe(II) was accelerated by photo-induced electrons from conduction band of the microspheres. And the π–π interaction between porphyrin and g-C3N4 also strikingly promoted the in-situ H2O2 production, which also boosted the Fenton-like process along with the IFCT effect. Stronger electron spin resonance signal of •OH confirmed the boost mentioned above and indicated that g-C3N4-porphyrin provided H2O2 in abundance for the Fenton-like process. This new Fenton-like catalyst exhibited superior oxidation performance and the optimum catalyst TFMS-CP0.1 achieved the removal of 92.6 % and 84.6 % towards phenol and hydroquinone in 3 h, respectively, and 88.2 % towards MO in 1 h. This work proposed a credible mechanism of visible light-induced Fenton-like process and achieved efficient oxidative degradation of the organic contaminant.

Biosolids-based catalyst for oxidative desulphurization of drop-in fuels derived from waste fats

In this work, the catalytic performance of a biosolids-based catalyst was tested in the oxidative desulphurization process of a model fuel solution containing benzothiophene ([S] of 500 ppm), as well as sulphur-rich products from a two-step thermal conversion process of brown grease to renewable hydrocarbons using biosolids as a water replacement during the hydrolysis step. The catalytic results of the biosolids-based material were compared with a classical Fenton-like reagent and a non-catalytic system. Biosolids-based catalyst outperformed the other systems at low temperature with a full desulphurization of benzothiophene solution achieved at 60 °C after 3 h and a good recyclability after four catalytic runs at 80 °C for 3 h. The desulphurization was less effective for hydrolysed fatty acids and crude pyrolysis oil derived from the conversion of brown grease to renewable hydrocarbons, which was due to the composition of the sulphur containing compounds, but still reached 87.7 ± 3.0 % and 74.7 ± 9.5 %, respectively.

Fe@Fe3O4/HKUST-1 composite: A Fenton-like agent with magnetic hyperthermia-enhanced chemodynamic therapy performance

Chemodynamic therapy (CDT) has attracted increasing attention, owing to its high tumor selectivity. However, the poor performance of Fenton or Fenton-like agents limits further clinical applications of this technique. Therefore, we developed a Fe@Fe3O4/Cu-trimesic acid metal organic frame (Fe@Fe3O4/HKUST-1) composite serving as a Fenton-like reagent with magnetic hyperthermia-enhanced chemodynamic performance. In the composite, Fe@Fe3O4 acts as a magnetic hyperthermia agent, while HKUST-1 serves as an excellent Fenton-like catalyst. The experimental results show that the magnetothermal effect of Fe@Fe3O4 in an alternating magnetic field can be used to enhance the chemodynamic performance of HKUST-1 in the composite. The Fe@Fe3O4/HKUST-1 composite exhibits great potential for application in magnetic hyperthermia-enhanced CDT.

Fenton-like degradation of carmine dyes based on artificial intelligence modeling and optimization of reduced graphene oxide loaded iron-cobalt-nickel trimetallic nanocomposites

In this experiment, reduced graphene oxide loaded iron-cobalt-nickel trimetallic nano compounds were prepared by co-precipitation method and coadministered with oxidant hydrogen peroxide to form Fenton-like reagents. The degradation of carmine dye simulated industrial wastewater by this type of fenton catalyst in combination with ultrasound was investigated and it can be identified that ultrasound is synergistic when combined with this type of fenton process. In this experiment, the synthesized nanocomposites were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, fourier transform infrared spectroscopy, raman spectroscopy, N2 adsorption, and superconducting quantum interferometry, and the results demonstrated that the materials have a typical graphite porous structure and excellent magnetic properties. The influences of four factors (V(H2O2), reaction time, initial concentration and catalyst dosage) on the degradation of carmine dye were further analyzed. The experiment was then modeled and optimized with response surfaces and artificial intelligence. Through the comparative analysis of the experimental value and the predicted value, it is found that the absolute error of the artificial neural network-particle swarm optimization model is the smallest, which indicates that the model makes a better prediction of the experimental results. The importance of influencing factors in the dye removal process was ranked according to F-test, random forest and Garson's formula, and it was discovered that V(H2O2) played the most dominant role. Finally, by a simple magnetic separation, the rGO/Fe/Co/Ni trimetallic nano compound was still retained 47% of its catalytic capacity after five consecutive recoveries using this catalyst and applying it to the next degradation experiment, which indicates its excellent reusability and reflects the outstanding degradation ability of this compounds.

Efficient methane production from waste activated sludge and Fenton-like pretreated rice straw in an integrated bio-electrochemical system

Integrated microbial electrolysis cell-anaerobic digestion (MEC-AD) systems have demonstrated potential advantages for methane production in the presence of small amounts of residual inhibitors. In this study, a series of tests were conducted to analyse the acidification and methanogenesis performance of pretreated rice straw (RS) in anaerobic digestion (AD) and MEC-AD systems after the addition of Fenton-like reagents. The results indicated that the short-chain acids (SCFAs) accumulations reached 2284.64 ± 21.57 mg COD/L with a dosage ratio of 1/4 (g RS/g VSS sludge) in the MEC-AD system and that methane production increased by 63.8% compared with that of an individual AD system. In the interim, the net energy output reached 1.09 × 103 J/g TCOD, which was 1.23 times higher than that of the AD system. The residual Fe3+/Fe2+ in the pretreatment reagent was capable of promoting acidification and methanogenesis in sludge and RS fermentation. The RS hydrolysis products could constrain methanogenesis, which can be mitigated by introducing an MEC. The microbiological analyses revealed that the MEC strongly increased the enrichment of hydrogenotrophic methanogens, especially Methanobacterium (61.16%). Meanwhile, the Syntrophomonas and Acetobacterium abundances increased to 2.81% and 2.65%, respectively, which suggested the reinforcement of acetogenesis and methanogenesis. Therefore, the enhanced hydrogenotrophic methanogens might have served as the key for enhancing the efficiency of methanogenesis due to the introduction of an MEC.