Iron–cobalt mixed oxide nanocatalysts: Heterogeneous peroxymonosulfate activation, cobalt leaching, and ferromagnetic properties for environmental applications

Sulfate radical-based advanced oxidation technologies (SR-AOTs) are attracting considerable attention due to the high oxidizing ability of SRs to degrade organic pollutants in aqueous environments. This study was carried out to respond to current concerns and challenges in SR-AOTs, including (i) need of heterogeneous activation of sulfate salts using transition metal oxides, (ii) nanoscaling of the metal oxide catalysts for high catalytic activity and promising properties with respect to leaching, and (iii) easy removal and recovery of the catalytic materials after their applications for water and wastewater treatments. In this study, we report a novel approach of using Fe–Co mixed oxide nanocatalysts for the heterogeneous activation of peroxymonosulfate (PMS) to generate SRs targeting the decomposition of 2,4-dichlorophenol, and especially focus on some synthesis parameters such as calcination temperature, Fe/Co contents, and TiO₂ support. The physicochemical properties of the catalysts were investigated using porosimetry, XRD, HR-TEM, H₂-TPR, and XPS. Ferromagnetic CoFe₂O₄ composites formed by thermal oxidation of a mixed phase of Fe and Co exhibited significant implications for the efficient and environmentally friendly activation of PMS, including (i) the cobalt species in CoFe₂O₄ are of Co(II), unlike Co₃O₄ showing some detrimental effects of Co(III) on the PMS activation, (ii) CoFe₂O₄ possesses suppressed Co leaching properties due to strong Fe–Co interactions (i.e. Fe–Co linkages), and (iii) Fe–Co catalysts in form of CoFe₂O₄ are easier to recover due to the unique ferromagnetic nature of CoFe₂O₄. In addition, the presence of Fe was found to be beneficial for enriching hydroxyl group content on the Fe–Co catalyst surface, which is believed to facilitate the formation of Co(II)-OH complexes that are vital for heterogeneous PMS activation.     

Simple fabrication of strongly coupled cobalt ferrite/carbon nanotube composite based on deoxygenation for improving lithium storage

An easy method to synthesize a strongly coupled cobalt ferrite/carbon nanotube (CoFe₂O₄/CNT) composite with oxygen bridges between CoFe₂O₄ and reduced carbon nanotubes (CNTs) by calcining the precursor material was reported. The precursor was prepared by an electrostatic self-assembly of the exfoliated Co(II)Fe(II)Fe(III)-layered double hydroxide (CoFeFe-LDH) nanosheets and acid treated CNTs. The deoxygenation effect of ferrous ion (Fe²⁺) in CoFeFe-LDH nanosheets on the oxygen-containing groups of acid treated CNTs was investigated by X-ray photoelectron spectroscopy (XPS) measurement. After thermal conversion, the obtained CoFe₂O₄ was bonded to the reduced CNTs through Metal–O–C (oxygen bridge), which was characterized by XPS, Fourier transform infrared spectroscopy, and Raman spectroscopy. When applied as an anode for lithium-ion battery, the CoFe₂O₄/CNT composite exhibited a low resistance of charge transfer and Li-ion diffusion, good cycle performance, and high rate capability. At a lower current density of 0.15 A·g⁻¹, a specific discharge capacity of 910 mA·h·g⁻¹ was achieved up to 50 cycles. When current density was increased to 8.8 A·g⁻¹, the CoFe₂O₄/CNT composite still delivered 500 mA·h·g⁻¹.     

Cobalt ferrite thin films as anode material for lithium ion batteries

Spinel cobalt ferrite (CoFe₂O₄) thin films have been fabricated by 355 nm reactive pulsed laser deposition on stainless steel substrates. XRD and SEM analyses showed that the CoFe₂O₄ films exhibited a polycrystalline structure and were composed of nanoparticles with an average size of 80 nm. At 1C rate, the initial irreversible capacity of polycrystalline CoFe₂O₄ film electrode cycled between 0.01 and 3.0 V reached 1280 mAh/g. After 20 cycles, the reversible discharge capacities decreased and sustained about 610 mAh/g. The diffusion coefficient of Li ion for CoFe₂O₄ films was determined by ac impedance method, and the average value was estimated to be 1.1 × 10⁻¹³ cm²/S. Based on ex situ XRD, SEM and XPS data, the electrochemical mechanism of CoFe₂O₄ film with lithium upon cycling was proposed. During the first discharge, the amorphization process of CoFe₂O₄ film electrode is accompanied with the reduction of Co²⁺ and Fe³⁺ into metal Co and Fe, respectively, and then the reversible oxidation/reduction processes of Co, Fe and Li₂O take place in the subsequent charge/discharge cycles.     

Cathodic behaviour of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel electrodes in alkaline medium

Spinel type CoFe₂O₄ thin films have been prepared, on stainless steel supports, by thermal decomposition of aqueous solutions of mixed cobalt and iron nitrates in 1:2 molar ratio at 400 °C. The electrochemical behaviour of the CoFe₂O₄/1 M KOH interface was investigated by cyclic voltammetry, chronoamperometry and impedance techniques. The studies allowed finding out the redox reactions occurring at the oxide surface. The results were compared with colloidal electrodes prepared by alkaline precipitation of Fe(II) or Fe(III) hydrous oxi-hydroxides on platinum electrodes. In addition, it has been concluded that the processes are diffusion-controlled and the diffusion of the hydroxide ion, through the oxide, acts as the rate-determining step. The diffusion coefficient of OH⁻ through the oxide film was determined using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy techniques.     

Mg and Cu incorporated CoFe2O4 catalyst: characterization and methane cracking performance for hydrogen and nano-carbon production

The Cobalt ferrite (CoFe₂O₄) and cobalt ferrite incorporated with Cu (Cu–CoFe₂O₄) and Mg (Mg–CoFe₂O₄) have been synthesized by wet chemical route. In fixed-bed reactor, the CoFe₂O₄, Cu–CoFe₂O₄ and Mg–CoFe₂O₄ were used as catalysts for direct cracking of methane at temperature of 800 °C and 20 mL/min of feed gas flow rate for hydrogen and nano-carbon production. Different characterizations techniques namely XRD, FESEM, XPS, Raman spectroscopy, TGA, BET for fresh and spent catalysts have been executed. The X-ray powder diffraction and Raman spectra confirmed that the fresh catalysts possess a cubic spinel crystal structure. The FESEM images for spent catalysts displayed that filamentous carbons were not formed over catalysts surfaces except a few amount was observed over the spent CoFe₂O₄ catalyst. XPS results confirmed the purity of the synthesized catalysts and qualitatively evaluate the cation distribution between the tetrahedral and octahedral sites from Co 2p_3/2 and Fe 2p_3/2 spectra. BET surface area revealed no significant effects in surface area and pore size of CoFe₂O₄ catalyst by incorporation of Mg and Cu metals. Activity studies showed that incorporation Mg metal on CoFe₂O₄ improved methane conversion up to 40.03% and hydrogen formation rate of 79.90 mol H₂ g⁻¹ min⁻¹ as compared to 31.61% and 66 mol H₂ g⁻¹ min⁻¹ for CoFe₂O₄ catalyst. Whilst, Cu metal incorporation in CoFe₂O₄ catalyst led to decline the catalyst performance. Structure activity relationship was described in details.     

Facile electrodeposition of MFe2O4 (M=Co,Fe) on carbon cloth as air cathodes for Li-O2 batteries

To develop high energy Li-O₂ batteries (LOBs), it is important to optimize the air cathode structure. Therefore, MFe₂O₄@carbon cloth (M = Co, Fe) has been prepared by electrodeposition to be an effective cathode for LOBs. This cathode can effectively avoid the disturbance of a polymer binder during the discharge-charge process. Electrocatalytic and electrochemical measurements show that MFe₂O₄@carbon cloth can enhance the ORR/OER kinetics. In particular, CoFe₂O₄@carbon cloth exhibits a good initial discharge specific capacity (7259 mA h/g at 170 mA/g) and long cycle life (over 100 cycles at the upper limit specific capacity of 500 mA h/g at 170 mA/g). The favorable electrocatalytic properties of CoFe₂O₄@CC are ascribed to the presence of Co²⁺.     

Oxidation of 4‐nitrophenol in water over Fe(III), Co(II), and Ni(II) impregnated MCM41 catalysts

BACKGROUND: Nitrophenols are toxic constituents of the effluents of petroleum, textile, dye, iron and steel, foundries, pharmaceutical and electrical manufacturing industries. Aromatic nitro compounds are particularly resistant to normal chemical or biological oxidation making them environmentally persistent. Advanced oxidation using appropriate catalysts mineralize these organics to harmless final products. In this work, MCM41‐based catalysts incorporating Fe(III)‐, Co(II)‐ and Ni(II)‐ cations were used for oxidizing 4‐nitrophenol in water under variable conditions of reaction time, pH, mole ratio of the reactant and the oxidant, catalyst load, feed concentration, and temperature. RESULTS: The catalysts prepared were characterized with X‐ray diffraction (XRD) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), cation exchange capacity (CEC) and atomic absorption spectrometry (AAS) measurements. In typical reaction conditions of temperature 353 K, time 300 min, catalyst load 2 g L^?1 and 10^?3 mol L^?1 4‐nitrophenol, the oxidation was 48.7, 52.2 and 55.2% with H₂O₂ and 42.5, 56.6 and 60.2% without H₂O₂ for Fe(III)‐, Co(II)‐ and Ni(II)‐MCM41, respectively. Pseudo‐first‐order kinetics with kinetic constant of 2.0 × 10^?3 to 5.5 × 10^?3 Lg^?1 min^?1 was proposed along with a possible mechanism. 4‐nitrocatechol, 4‐nitropyrogallol, 1,2,4‐trihydroxybenzene, hydroquinone, acrylic acid, malonic acid, and oxalic acid were identified in the oxidation products. CONCLUSION: Introduction of Fe(III)‐, Co(II)‐ and Ni(II)‐ into MCM‐41 by impregnation produced effective catalysts for wet oxidation of 4‐nitrophenol. The catalysts were able to oxidize 4‐NP even without the presence of an oxidizing agent. The results suggest that the transition metal loaded MCM41 brings about a more effective interaction between 4‐NP molecules and OH radicals. Copyright © 2008 Society of Chemical Industry     

Oil-Refinery Wastewater Treatment Aiming Reuse by Advanced Oxidation Processes (AOPs) Combined with Biological Activated Carbon (BAC)

The treatment of a refinery wastewater by Advanced Oxidation Processes (AOP) coupled with Biological Activated Carbon (BAC) was investigated aiming to generate water for reuse. O₃/UV and H₂O₂/UV processes were employed to oxidize the organic matter and the BAC process to remove residual organic matter from the AOP effluent. AOP promoted oxidation of recalcitrant organic matter as observed by moderate drops on the treated wastewater absorbance (31–79%) and TOC values (10–18%). BAC filters showed to be effective, reaching average efficiencies of 65% in a sufficiently long period of operation (84 days), while GAC filters were saturated after 28 days. Effluent TOC values in the range of 4 to 8.5 mg/L were achieved by the combined treatment (H₂O₂/UV + BAC), allowing water reuse.     

Phenol methylation over nanoparticulate CoFe2O4 inverse spinel catalysts: The effect of morphology on catalytic performance

A series of CoFe₂O₄ nanoparticles have been prepared via co-precipitation and controlled thermal sintering, with tunable diameters spanning 7–50 nm. XRD confirms that the inverse spinel structure is adopted by all samples, while XPS shows their surface compositions depend on calcination temperature and associated particle size. Small (<20 nm) particles expose Fe³⁺ enriched surfaces, whereas larger (50 nm) particles formed at higher temperatures possess Co:Fe surface compositions close to the expected 1:2 bulk ratio. A model is proposed in which smaller crystallites expose predominately (1 1 1) facets, preferentially terminated in tetrahedral Fe³⁺ surface sites, while sintering favours (1 1 0) and (1 0 0) facets and Co:Fe surface compositions closer to the bulk inverse spinel phase. All materials were active towards the gas-phase methylation of phenol to o-cresol at temperatures as low as 300 °C. Under these conditions, materials calcined at 450 and 750 °C exhibit o-cresol selectivities of 90% and 80%, respectively. Increasing either particle size or reaction temperature promotes methanol decomposition and the evolution of gaseous reductants (principally CO and H₂), which may play a role in CoFe₂O₄ reduction and the concomitant respective dehydroxylation of phenol to benzene. The degree of methanol decomposition, and consequent H₂ or CO evolution, appears to correlate with surface Co²⁺ content: larger CoFe₂O₄ nanoparticles have more Co rich surfaces and are more active towards methanol decomposition than their smaller counterparts. Reduction of the inverse spinel surface thus switches catalysis from the regio- and chemo-selective methylation of phenol to o-cresol, towards methanol decomposition and phenol dehydroxylation to benzene. At 300 °C sub-20 nm CoFe₂O₄ nanoparticles are less active for methanol decomposition and become less susceptible to reduction than their 50 nm counterparts, favouring a high selectivity towards methylation.     

The effect of reaction temperature on the structural and magnetic properties of nano CoFe2O4

Nano cobalt ferrites (CoFe₂O₄) were co-precipitated at various reaction temperatures (60, 70 and 80 °C) for 1 h. The reaction temperature greatly influenced the crystallite size and the magnetic behaviours of the nano CoFe₂O₄. The mean crystallite size ranged from 9 to 15 nm with the increase in the reaction temperature and the intensity of metal oxide vibrations at 568–550 cm⁻¹ were also inclined. The synthesized samples were in the stoichiometric ratio of 1:2 (Co:Fe) with roughly spherical morphology. The synthesized cobalt nanoferrites exhibited ferromagnetism at room temperature and 5 K, and the saturation magnetization increased from 6.4 to 20 emu/g with the crystallite size.     

Impact of rare earth europium (RE-Eu3+) ions substitution on microstructural,optical and magnetic properties of CoFe2−xEuxO4 nanosystems

In this study, pure cobalt ferrite (CoFe₂O₄) nanoparticles and europium doped CoFe₂O₄ (CoFe_2−xEu_xO₄; x = 0.1, 0.2, 0.3) nanoparticles were synthesized by the precipitation and hydrothermal approach. The impact of replacing trivalent iron (Fe³⁺) ions by trivalent rare earth europium (RE-Eu³⁺) ions on the microstructure, optical and magnetic properties of the produced CoFe₂O₄ nanoparticles was studied. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectra exposed the consistency of a single cubic phase with the evidence of Eu₂O₃ phases for x ≥ 0.2. FTIR transmittance spectra showed that, the all investigated samples have three characteristic metal-oxygen bond vibrations corresponding to octahedral B-site (υ₁ and υ₂) and tetrahedral A-site (υ₃) around 415 cm⁻¹, 470 cm⁻¹ and 600 cm⁻¹ respectively. XRD and energy dispersive X-ray spectroscopy studies affirmed the integration of RE-Eu³⁺ ions within CoFe₂O₄ host lattice and decrease of average crystals size from 13.7 nm to 4.7 nm. Transmission electron microscopy (TEM) analysis showed the crucial role played by RE-Eu³⁺ added to CoFe₂O₄ in reducing the particle size below 5 nm in agreement with XRD analysis. High resolution-TEM (HR-TEM) analysis showed that the as-synthesized spinel ferrite, i.e., CoFe_2−xEu_xO₄, nanoparticles are single-crystalline with no visible defects. In addition, the HR-TEM results showed that pure and doped CoFe₂O₄ have well-resolved lattice fringes and their interplanar spacings matches that obtained by XRD analysis. Magnetic properties investigated by the vibrating sample magnetometer technique illustrated transformation of magnetic state from ferromagnetic to superparamagnetic at 300 K resulting in introducing RE-Eu³⁺ in CoFe₂O₄ lattice. At low temperature (~5 K) the magnetic order was ferromagnetic for both pure and doped CoFe₂O₄ samples. Substitution of Fe³⁺ ions in CoFe₂O₄ nanoparticles with RE-Eu³⁺ ions optimizes the sample nanocrystals size, cation distribution and magnetic properties for many applications.     

Effects of O2 on aqueous SO2 leaching of Co,Cu and Ni from discard smelter slag

In the leaching of non‐ferrous smelter slag with a dissolved gas mixture of SO₂ and O₂, the behaviour of Co, Cu, Ni, Zn and Fe was studied in a 1‐L batch reactor. The parameters investigated include P_SO2, P_O2, temperature, particle size and pH. Co, Zn and Fe behaved similarly while Ni and Cu displayed distinguishable characters. The addition of O₂ prevented the precipitation of Cu after dissolution, and increased acidity of the leaching solution. The increase in acid strength resulted in an increase in the extraction of Co, Zn and Fe. The effect of acidity on Cu and Ni extraction was however much weaker. The combination of SO₂ and O₂ was found to be a more effective oxidant of Fe(II) to Fe(III) than O₂ alone. Simultaneous extraction of valuable metals and removal of Fe could be achieved by leaching at pH of 3 to 4. Maximum selectivities obtained for Co, Ni and Cu over Fe were 300, 2000 and 4000, respectively.     

Synergistic effect in structural and supercapacitor performance of well dispersed CoFe2O4/Co3O4 nano-hetrostructures

Herein, we report a facile homogeneous urea – assisted hydrothermal approach for the design of CoFe₂O₄/Co₃O₄ nano hetrostructure. A variation in Co concentration leads to smartly designed composite material namely CFC-11 and CFC-12 where CFC-12 appreciates the benefits of both CoFe₂O₄ and Co₃O₄ nanoparticles. The physico – chemical properties of as developed materials were investigated by X-ray diffraction (XRD), field emission electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), X-ray photoelectron microscopy (XPS) and Raman spectroscopy. The specific surface area and pore size distribution was determined by Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halendo (BJH) respectively. Magnetic measurements via. vibrating sample magnetometer (VSM) demonstrate that saturation magnetization decreases with the incorporation of Co₃O₄ antiferromagnetic nanoparticles. To explore the utility of as designed nano-hetrostructures as supercapacitor electrodes, we employed cyclic voltammetry (CV) and electrochemical impedence spectroscopy (EIS) measurements. A high specific capacitance of 761.1?F?g^?1 at 10?mV?s^?1, admirable cyclic durability of 92.2% and a low resistance value obtained from impedence measurements was observed for CFC-12. The favorable performance demonstrates the synergistic effect of CoFe₂O₄ and Co₃O₄ nanoparticles and thus promise an excellent material for energy storage devices.     

Chemical and electrochemical considerations on the removal process of hexavalent chromium from aqueous media

Two methods were used to remove Cr(VI) from industrial wastewater. Although both are based in the same general reaction: 3Fe(II)_(aq) + Cr(VI)_(aq) ; 3Fe(III)_(aq) + Cr(III)_(aq) the way in which the required amount of Fe(II) is added to the wastewater is different for each method. In the chemical method, Fe(II)_(aq) is supplied by dissolving FeSO₄ · 7(H₂O)_(s) into the wastewater, while in the electrochemical process Fe(II)_(aq) ions are formed directly in solution by anodic dissolution of an steel electrode. After this reduction process, the resulting Cr(III)_(aq) and Fe(III)_(aq) ions are precipitated as insoluble hydroxide species, in both cases, changing the pH (i.e., adding Ca(OH)_2(s)). Based on the chemical and thermodynamic characteristics of the systems Cr(VI)–Cr(III)–H₂O–e^– and Fe(III)–Fe(II)–H₂O–e^– both processes were optimized. However we show that the electrochemical option, apart from providing a better form of control, generates significantly less sludge as compared with the chemical process. Furthermore, it is also shown that sludge ageing promotes the formation of soluble polynuclear species of Cr(III). Therefore, it is recommended to separate the chromium and iron-bearing phases once they are formed. We propose the optimum hydraulic conditions for the continuous reduction of Cr(VI) present in the aqueous media treated in a plug-flow reactor.     

Indirect cathodic electrocatalytic degradation of dimethylphthalate with PW11O39Fe(III)(H2O) and H2O2 in neutral aqueous medium

Cyclic voltammetry and degradation of dimethylphthalate (DMP) revealed that the iron-substituted heteropolytungstate anion PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ is an excellent indirect cathodic oxidative electrocatalyst in the presence of H₂O₂. PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ can electrocatalyze the reduction of H₂O₂ to hydroxyl radicals via an inner-sphere electron transfer mechanism, which cause oxidative decomposition of DMP. Almost complete DMP removal and ca. 30% mineralization were obtained in less than 120 min in a mixed phosphate solution at pH 6.86 containing 0.1 mM DMP. MS analyses of the intermediates and final products suggested that glyoxal, oxalic acid and acetic acid are the main ring-opening products, besides some unstable hydroxylated aromatic intermediates. The effects of added H₂O₂ concentration, applied cathodic potential and DMP initial concentration on the degradation of DMP were also investigated. A concentration of 1.0 mM H₂O₂ and cathodic potential of −0.3 V were optimal conditions for DMP degradation in our experiments. At higher initial DMP concentrations degradation also occurred, but at a slower decay rate compared to lower initial concentrations. The present system thus represents a possible method to use PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ as an indirect cathodic oxidative electrocatalyst in water and wastewater treatment.     

Impact of Zn doping on the dielectric and magnetic properties of CoFe2O4 nanoparticles

Owing to its unique magnetic, dielectric, electrical and catalytic properties, ferrite nanostructure materials gain vital importance in high frequency, memory, imaging, sensor, energy and biomedical applications. Doping is one of the strategies to manipulate the spinel ferrite structure, which could alter the physico-chemical properties. In the present work, Co_1-xZn_xFe₂O₄ ($x$ = 0, 0.1, 0.2, 0.3, and 0.4 wt%) nanoparticles were prepared by sol-gel auto-combustion method and its structural, morphological, vibrational, optical, electrical and magnetic properties were studied. The structural analysis affirms the single-phase cubic spinel structure of CoFe₂O₄. The crystallite size, lattice constant, unit cell, X-ray density, dislocation density and hopping length were significantly varied with Zn doping. The Fe–O stretching vibration was estimated by FTIR and Raman spectra. TEM micrographs show the agglomerated particles and it size varies between 10 and 56 nm. The Hall effect measurement shows the switching of charge carriers from n to p type. The dielectric constant (ε′) varies from 0.2 × 10³ to 1.2 × 10³ for different Zn doping. The VSM analysis shows relatively high saturation magnetization of 57 and 69 emu/g for ZC 0.1 and ZC 0.2 samples, respectively than that of undoped sample. All the prepared samples exhibit soft magnetic behaviour. Hence, it can be realized that the lower concentration of Zn ion doping significantly alters the magnetic properties of CoFe₂O₄ through variation in the cationic distribution and exchange interaction between the Co and Fe sites of the inverse spinel structure of CoFe₂O_4.     

Sewage sludge treatment using microwave‐enhanced advanced oxidation processes with and without ferrous sulfate addition

BACKGROUND: Microwave‐enhanced advanced oxidation processes with and without the addition of ferrous sulfate (MW/H₂O₂/Fe²⁺‐AOP and MW/H₂O₂‐AOP respectively) were studied for reduction of solids and solubilisation of nutrients from secondary sewage sludge. RESULTS: For the MW/H₂O₂/Fe²⁺‐AOP the yields of solubilisation of orthophosphate and ammonia decreased with increasing temperature. The best results (88.1 mg L^?1 for orthophosphate and 22.7 mg L^?1 for ammonia) were obtained at a treatment temperature of 40 °C. In contrast, the MW/H₂O₂‐AOP had an advantage when it was operated at higher temperatures of 60 and 80 °C. The highest yields of solubilisation were obtained at 60 °C for orthophosphate (81.1 mg L^?1) and at 80 °C for both ammonia (35.0 mg L^?1) and soluble chemical oxygen demand (1954 mg L^?1). Over the temperature range used in this study, the MW/H₂O₂‐AOP gave a better performance than the MW/H₂O₂/Fe²⁺‐AOP. CONCLUSION: For sewage sludge treatment the MW/H₂O₂‐AOP is more effective than the MW/H₂O₂/Fe²⁺‐AOP in terms of solid reduction and nutrient solubilisation. It will also be more cost‐effective, as it does not require iron addition in the process. Copyright © 2008 Society of Chemical Industry     

Treatment of paper and pulp wastewater and removal of odorous compounds by a Fenton‐like process at the pilot scale

A Fenton‐like process, involving oxidation and coagulation, was evaluated for the removal of odorous compounds and treatment of a pulp and paper wastewater. The main parameters that govern the complex reactive system [pH and Fe(III) and hydrogen peroxide concentrations] were studied. Concentrations of Fe(III) between 100 and 1000 mg L^?1 and of H₂O₂ between 0 and 2000 mg L^?1 were chosen. The main mechanism for color removal was coagulation. The maximum COD, color and aromatic compound removals were 75, 98 and 95%, respectively, under optimal operating conditions ([Fe(III)] = 400 mg L^?1; [H₂O₂] = 500–1000 mg L^?1; pH = 2.5; followed by coagulation at pH 5.0). The biodegradability of the wastewater treated increased from 0.4 to 0.7 under optimal conditions and no residual hydrogen peroxide was found after treatment. However, partially or non‐oxidized compounds present in the treated wastewater presented higher acute toxicity to Artemia salina than the untreated wastewater. Based on the optimum conditions, pilot‐scale experiments were conducted and revealed a high efficiency in relation to the mineralization of organic compounds. Terpenes [(1S)‐α‐pinene, β‐pinene, (1R)‐α‐pinene and limonene] were identified in the wastewater and were completely eliminated by the Fenton‐like treatment. Copyright © 2006 Society of Chemical Industry     

High capacity three-dimensional ordered macroporous CoFe2O4 as anode material for lithium ion batteries

A three-dimensional ordered macroporous (3DOM) cobalt ferrite (CoFe₂O₄) was prepared using polystyrene (PS) colloidal crystal template. The scanning electron microscopy (SEM) and the transmission electron microscopy (TEM) micrographs showed that the as-prepared CoFe₂O₄ material had a typical 3DOM structure, which was constructed with about 130 nm-sized macropores and 10-20 nm-sized walls. The obtained CoFe₂O₄ material had a specific surface area of 66.67 m² g⁻¹, and could deliver a relatively high capacity of 702 mAh g⁻¹ (about double that of graphite) at a current density of 0.2 mA cm⁻² after 30 cycles. Owing to the 3DOM nanoarchitecture, the as-prepared CoFe₂O₄ electrode exhibited a good rate performance. The results suggest a promising application of the 3DOM CoFe₂O₄ as anode material for lithium ion batteries.     

Magnetoelectric response and tunneling magnetoresistance behavior of flexible P(VDF-H FP)/Cobalt ferrite nanofiber composite films

Fabrication of magnetoelectric (ME) polymer composite films by embedding ferromagnetic cobalt ferrite (CoFe₂O₄) nanofibers into electroactive poly(vinylidene fluoride–hexafluoropropylene) (P(VDF-HFP)) matrix is reported. Single-phase CoFe₂O₄ nanofibers made of cubic spinel nano crystallites are synthesized by using electro-spinning method, whereas the solution-casting technique is adapted to prepare flexible polymer composite films. The influence of CoFe₂O₄ nanofiber on structural, functional, magnetic, ferroelectric, and magnetoresistance properties of the composite films is investigated. The cross-coupling between ferroelectric and ferromagnetic orderings is ensured, by the variations of ferroelectric response at different magnetic fields. These magnetoelectric films are found to exhibit a negative tunneling magnetoresistance (TMR) effect with maximum TMR% of 28 for the film with 20 wt% of CoFe₂O₄ loading. The dielectric constant and electrical energy storage density of the films are increased with the addition of CoFe₂O₄ nanofiber. The ME films exhibiting TMR and high energy density can be the potential candidates for multifunctional device applications such as memory and spintronics devices, magnetic sensor, and bio-sensor.