Insight mechanism of magnetic activated catalyst derived from recycled steel residue for black liquor degradation.

The present work deals with developing a method for revalorizing steel residues to create sunlight-active photocatalysts based on iron oxides. Commercial-grade steel leftovers are oxidized under different combinations of pH and temperature (50-90 °C and 3 ≥ pH ≤ 5) in a low energy-intensive setup. The material with the highest production efficiency (yield > 12%) and magnetic susceptibility (χm = 387 × 10-6 m3/kg) was further explored and modified by diffusion of M2+ (Zn and Co) ions within the structure of the oxide using a hydrothermal method to create ZnFe2O4, CoFe2O4 and combined Co-Zn ferrite. (Co-Zn)Fe2O4 displayed a bandgap of 2.02 eV and can be activated under sunlight irradiation. Electron microscopy studies show that (Co-Zn)Fe2O4 consists of particles with diameters between 400 and 700 nm, homogeneous size, even distribution, and good dispersibility. Application of the developed materials in the sunlight catalysis of black liquors from cellulose extraction resulted in a reduction of the Chemical Oxygen Demand (- 15% on average) and an enhancement in biodegradability (> 0.57 BOD/COD) after 180 min of reaction. Since the presented process employs direct solar light, it opens the possibility to large-scale water treatment and chemical upgrading applications.

Structural Characterization and Magnetic Behavior Due to the Cationic Substitution of Lanthanides on Ferrite Nanoparticles.

A new series of [Fe3-xLnx]O4 nanoparticles, with Ln = Gd; Dy; Lu and x = 0.05; 0.1; 0.15, was synthesized using the coprecipitation method. Analyses by X-ray diffraction (XRD), Rietveld refinement, and high-resolution transmission electron microscopy (HRTEM) indicate that all phases crystallized in space group Fd3¯m, characteristic of spinels. The XRD patterns, HRTEM, scanning electron microscopy analysis (SEM-EDS), and Raman spectra showed single phases. Transmission electron microscopy (TEM), Rietveld analysis, and Scherrer's calculations confirm that these materials are nanoparticles with sizes in the range of ~6 nm to ~13 nm. Magnetic measurements reveal that the saturation magnetization (Ms) of the as-prepared ferrites increases with lanthanide chemical substitution (x), while the coercivity (Hc) has low values. The Raman analysis confirms that the compounds are ferrites and the Ms behavior can be explained by the relationship between the areas of the signals. The magnetic measurements indicate superparamagnetic behavior. The blocking temperatures (TB) were estimated from ZFC-FC measurements, and the use of the Néel equation enabled the magnetic anisotropy to be estimated.

Sustainable Cellulose Nanofibers-Mediated Synthesis of Uniform Spinel Zn-Ferrites Nanocorals for High Performances in Supercapacitors.

Spinel ferrites are versatile, low-cost, and abundant metal oxides with remarkable electronic and magnetic properties, which find several applications. Among them, they have been considered part of the next generation of electrochemical energy storage materials due to their variable oxidation states, low environmental toxicity, and possible synthesis through simple green chemical processing. However, most traditional procedures lead to the formation of poorly controlled materials (in terms of size, shape, composition, and/or crystalline structure). Thus, we report herein a cellulose nanofibers-mediated green procedure to prepare controlled highly porous nanocorals comprised of spinel Zn-ferrites. Then, they presented remarkable applications as electrodes in supercapacitors, which were thoroughly and critically discussed. The spinel Zn-ferrites nanocorals supercapacitor showed a much higher maximum specific capacitance (2031.81 F g-1 at a current density of 1 A g-1) than Fe2O3 and ZnO counterparts prepared by a similar approach (189.74 and 24.39 F g-1 at a current density of 1 A g-1). Its cyclic stability was also scrutinized via galvanostatic charging/discharging and electrochemical impedance spectroscopy, indicating excellent long-term stability. In addition, we manufactured an asymmetric supercapacitor device, which offered a high energy density value of 18.1 Wh kg-1 at a power density of 2609.2 W kg-1 (at 1 A g-1 in 2.0 mol L-1 KOH electrolyte). Based on our findings, we believe that higher performances observed for spinel Zn-ferrites nanocorals could be explained by their unique crystal structure and electronic configuration based on crystal field stabilization energy, which provides an electrostatic repulsion between the d electrons and the p orbitals of the surrounding oxygen anions, creating a level of energy that determines their final supercapacitance then evidenced, which is a very interesting property that could be explored for the production of clean energy storage devices.

Removal of pharmaceuticals from aqueous medium by alginate/polypyrrole/ZnFe2O4 beads via magnetic field enhanced adsorption.

The physicochemical and structural characteristics of the magnetic materials can be modulable due to exposition to a magnetic field, which allows, for example, to enhance its adsorption performance. In this sense, this study describes the preparation of magnetic beads of alginate/polypyrrole/ZnFe2O4 (Alg/PPy/ZnFe2O4) and investigates the effect of an external magnetic field (EMF) on their adsorption performance towards two overconsumed drugs, acetaminophen (ACT) and ibuprofen (IBU). Characterization analyses confirmed the composite formation and magnetic nature of Alg/PPy/ZnFe2O4. Conversely to the pristine beads (Alg/PPy), the presence of an EMF altered the swelling and pHPZC behavior of the magnetic beads, indicating that these properties are affected by this external stimulus. Batch experiments revealed that the amount of ACT and IBU adsorbed by Alg/PPy/ZnFe2O4 in 60-70 min is appreciably high (106.7 ad 108.2 mg/g). The presence of an EMF modulated the structure of Alg/PPy/ZnFe2O4 beads enhancing their adsorption capacity towards ACT and IBU by 14% and 12% compared to Alg/PPy. Kinetic analysis revealed that the adsorption of both drugs on Alg/PPy/ZnFe2O4 followed a pseudo-second-order. Besides, the adsorption mechanism was fitted by the Freundlich isotherm. Reuse experiments showed that the magnetic beads keep a high adsorption capacity for both drugs even after ten consecutive reuse cycles. The results presented here suggest that magnetic-responsive materials like Alg/PPy/ZnFe2O4 are prominent and modulable tools for improving the treatment of water/wastewater containing this class of contaminants.

MXene/Ferrite Magnetic Nanocomposites for Electrochemical Supercapacitor Applications.

MXene has been identified as a new emerging material for various applications including energy storage, electronics, and bio-related due to its wider physicochemical characteristics. Further the formation of hybrid composites of MXene with other materials makes them interesting to utilize in multifunctional applications. The selection of magnetic nanomaterials for the formation of nanocomposite with MXene would be interesting for the utilization of magnetic characteristics along with MXene. However, the selection of the magnetic nanomaterials is important, as the magnetic characteristics of the ferrites vary with the stoichiometric composition of metal ions, particle shape and size. The selection of the electrolyte is also important for electrochemical energy storage applications, as the electrolyte could influence the electrochemical performance. Further, the external magnetic field also could influence the electrochemical performance. This review briefly discusses the synthesis method of MXene, and ferrite magnetic nanoparticles and their composite formation. We also discussed the recent progress made on the MXene/ferrite nanocomposite for potential applications in electrochemical supercapacitor applications. The possibility of magnetic field-assisted supercapacitor applications with electrolyte and electrode materials are discussed.

Sunlight powered degradation of pentoxifylline Cs0.5Li0.5FeO2 as a green reusable photocatalyst: Mechanism, kinetics and toxicity studies.

The degradation of Pentoxifylline (PXF) was achieved successfully by green energy in a built-in solar photocatalytic system using hybrid LiCs ferrites (Li0.5Cs0.5FeO2) as magnetically recoverable photocatalysts. Kinetics showed a first-order reaction rate with maximum PXF removal of 94.91% at mildly acidic pH; additionally, the ferromagnetic properties of catalyst allowed recovery and reuse multiple times, reducing costs and time in degradation processes. The degradation products were identified by HPLC-MS and allowed us to propose a thermodynamically feasible mechanism that was validated through DFT calculations. Additionally, toxicity studies have been performed in bacteria and yeast where high loadings of Cs showed to be harmful to Staphylococcus aureus (MIC≥ 4.0 mg/mL); Salmonella typhi (MIC≥ 8.0 mg/mL) and Candida albicans (MIC≥ 10.0 mg/mL). The presented setup shows effectiveness and robustness in a degradation process using alternative energy sources for the elimination of non-biodegradable pollutants.

Radiosensitizing effects of citrate-coated cobalt and nickel ferrite nanoparticles on breast cancer cells.

Aim: Evaluation of the biocompatibility and radiosensitizer potential of citrate-coated cobalt (cit-CF) and nickel (cit-NF) ferrite nanoparticles (NPs). Materials & methods: Normal fibroblast and breast cancer cells were treated with different concentrations of citrate-coated ferrite NPs (cit-NPs) and irradiated with a cobalt-60 source at doses of 1 and 3 Gy. After 24 h, cell metabolism, morphology alterations and nanoparticle uptake were evaluated. Results: Cit-CF and cit-NF NPs showed no toxicity to normal cells up to 250 and 100 µg.ml-1, respectively. Combination of cit-NP and ionizing radiation resulted in up to fivefold increase in the radiation therapeutic efficacy against breast cancer cells. Conclusion: Cit-CF and cit-NF NPs are suitable candidates for application as breast cancer cell radiosensitizers.

Visible light activated magnetic photocatalysts for water treatment.

Environmental concerns have been raised regarding the intense contamination of water resources. Currently, numerous contaminants that reach water bodies are not efficiently removed by conventional water treatment methods. Therefore, there arises the need for development and optimization of efficient treatment methods for the removal of such recalcitrant contaminants. Given the circumstances, the present study aims to use of advanced oxidative processes for dye degradation. For this purpose, copper and zinc doped cobalt ferrites were synthesized by coprecipitation, targeting the degradation of methylene blue dye. The photocatalysts were characterized by XRD, WD-XRF, FE-SEM, N2 physisorption isotherms, UV-Vis diffuse reflectance spectroscopy, molecular fluorescence spectroscopy and zeta potential. According to the investigation of the degradation mechanism, the holes and hydroxyl radicals were mainly responsible for the dye's degradation. The obtained photocatalysts displayed promising results with up to 99% of dye degradation, employing conventional visible LED lamps, making the practical use of the catalyst highly viable, as well as the economic matters. Additionally, the synthesized materials' magnetic properties allowed total and efficient separation of the catalyst for its reutilization up to 4 cycles, with no decrease in photocatalytic activity and with low leaching of iron ions to solution.

Elimination of Escherichia coli in Water Using Cobalt Ferrite Nanoparticles: Laboratory and Pilot Plant Experiments.

This paper focuses on the synthesis of cobalt ferrite nanoparticles by the sol-gel method and their photocatalytic activity to eliminate bacteria in aqueous media at two different scales: in a laboratory reactor and a solar pilot plant. Cobalt ferrite nanoparticles were prepared using Co(II) and Fe(II) salts as precursors and cetyltrimethyl ammonium bromide as a surfactant. The obtained nanoparticles were characterized by X-ray diffraction, scanning and transmission electron microscopy. Escherichia coli (E. coli) strain ATCC 22922 was used as model bacteria for contact biocidal analysis carried out by disk diffusion method and photocatalysis under an ultraviolet A (UV-A) lamp for laboratory analysis and solar radiation (radiation below 350 W/m2 in a typical cloudy day) for the pilot plant analysis. The results showed that cobalt ferrite nanoparticles have an average diameter of (36 ± 20) nm and the X-ray diffraction pattern shows a cubic spinel structure. Using the disk diffusion technique, it was obtained inhibition zones of (17 ± 2) mm diameter. Results confirm the photocatalytic elimination of E. coli in water samples with remaining bacteria below 1% of the initial concentration during the experiment time (30 min for laboratory tests and 1.5 h for pilot plant tests).

Employing Calcination as a Facile Strategy to Reduce the Cytotoxicity in CoFe2O4 and NiFe2O4 Nanoparticles.

CoFe2O4 and NiFe2O4 nanoparticles (NPs) represent promising candidates for biomedical applications. However, in these systems, the knowledge over how various physical and chemical parameters influence their cytotoxicity remains limited. In this article, we investigated the effect of different calcination temperatures over cytotoxicity of CoFe2O4 and NiFe2O4 NPs, which were synthesized by a sol-gel proteic approach, toward L929 mouse fibroblastic cells. More specifically, we evaluated and compared CoFe2O4 and NiFe2O4 NPs presenting low crystallinity (that were calcined at 400 and 250 °C, respectively) with their highly crystalline counterparts (that were calcined at 800 °C). We found that the increase in the calcination temperature led to the reduction in the concentration of surface defect sites and/or more Co or Ni atoms located at preferential crystalline sites in both cases. A reduction in the cytotoxicity toward mouse fibroblast L929 cells was observed after calcination at 800 °C. Combining with inductively coupled plasma mass spectrometry data, our results indicate that the calcination temperature can be employed as a facile strategy to reduce the cytotoxicity of CoFe2O4 and NiFe2O4, in which higher temperatures contributed to the decrease in the dissolution of Co2+ or Ni2+ from the NPs. We believe these results may shed new insights into the various parameters that influence cytotoxicity in ferrite NPs, which may pave the way for their widespread applications in biomedicine.

Magnetic properties of liquid-phase sintered CoFe2O4 for application in magnetoelastic and magnetoelectric transducers.

Cobalt ferrite is a ferrimagnetic magnetostrictive ceramic that has potential application in magnetoelastic and magnetoelectric transducers. In this work, CoFe(2)O(4) was obtained using a conventional ceramic method and Bi(2)O(3) was used as additive in order to obtain liquid-phase sintered samples. Bi(2)O(3) was added to the ferrite in amounts ranging from 0.25 mol% to 0.45 mol% and samples were sintered at 900 °C and 950 °C. It was observed the presence of Bi-containing particles in the microstructure of the sintered samples and the magnetostriction results indicated microstructural anisotropy. It was verified that it is possible to get dense cobalt ferrites, liquid-phase sintered, with relative densities higher than 90% and with magnetostriction values very close to samples sintered without additives.