The oxidation of Fe(II) with Cu(II) in acidic sulfate solutions with air at elevated pressures

The oxidation of ferrous ions in acidic sulfate solutions in the presence of cupric ions at elevated air pressures was investigated in a high-intensity gas–liquid contactor. The study was required for the design of the regeneration steps of the novel Vitrisol^® desulphurization process. The effects of the Fe²⁺ concentration, Cu²⁺ concentration, Fe³⁺ concentration, initial H₂SO₄ concentration, and partial oxygen pressure on the reaction rate were determined at three different temperatures, i.e., T?=?50?°C, 70?°C, and 90?°C. Most of the experiments were determined to be affected by the mass transfer of oxygen, and therefore true intrinsic kinetics could not be fully determined. An increase in Fe²⁺ and Cu²⁺ concentrations, as well as the partial pressure of oxygen and temperature, increased the Fe²⁺ oxidation rate. H₂SO₄ did not influence the Fe²⁺ oxidation rate. An increase in Fe³⁺ concentration decreased the Fe²⁺ oxidation rate. Although determined from experiments partially affected by mass transfer, a first order of reaction in Fe²⁺ was observed, fractional orders in both Cu²⁺ and O₂ were measured, a zero order in H₂SO₄ was determined, and a negative, fractional order in Fe³⁺ was obtained. The activation energy was estimated to be 31.3?kJ/mol.     

Effect of Hydrogen Treatment on the Catalytic Activity of Iron Oxide Based Materials Dispersed Over Activated Carbon: Investigations Toward Hydrogen Peroxide Decomposition

The effect of hydrogen treatment (400 °C/1 h) on the catalytic properties toward H₂O₂ decomposition of iron oxide based materials dispersed over activated carbon were investigated. Two different supports were evaluated: a commercial activated carbon (ACM) and an activated carbon produced from spent coffee grounds (ACR). The catalysts were characterized using XRD, SEM, N₂-sorption, XPS and TPR analysis. The main results suggest the formation of composites with high surface area (>800 m² g^?1) and the hydrogen treatment resulted in a great increase in the catalytic activity, probably as a function of the reduced iron species (Fe²⁺ and Fe⁰) formed with the treatment. Moreover, the catalyst prepared with ACR showed to be more active than that prepared from ACM.     

Elucidating the Effect of Iron Speciation (Fe2+/Fe3+) on Crystallization Kinetics of Sodium Aluminosilicate Glasses

We report on the influence of Fe₂O₃ on the crystallization kinetics of nepheline (Na₂O·Al₂O₃·2SiO₂)‐based sodium aluminosilicate glasses. A series of glasses with varying Al₂O₃/Fe₂O₃ content were synthesized in the system 25Na₂O–(25–x) Al₂O₃–xFe₂O₃–50SiO₂ (x varies between 0 and 5 mol%) through melt‐quench technique. A systematic set of experiments were performed to elucidate the influence of iron speciation (Fe²⁺/Fe³⁺) on the crystallization kinetics of these glasses including: (1) obtaining the details of nonisothermal crystallization kinetics by differential scanning calorimetry, (2) determining the influence of heat treatment on the structure and iron coordination in glasses by X‐ray photoelectron spectroscopy and wet chemistry, and (3) following the crystalline phase evolution in glasses in air and inert environments by X‐ray diffraction and scanning electron microscopy. The crystallization of two polymorphs of NaAlSiO₄—carnegieite (orthorhombic) and nepheline (hexagonal)—was observed in all the glasses, wherein the incorporation of iron promotes the formation of nepheline over carnegieite while shifting the crystallization mechanism from surface to volume. The influence of environment (air versus inert) and iron content on the crystallization kinetics of these glasses is contextualized from the perspective of the devitrification problem usually observed in sodium‐ and alumina‐rich high level nuclear waste glasses.     

The electrochemical behaviour of iron oxides in dilute sulphuric acid and the interpretation of the flade potential of iron

The cathodic reduction of Fe₂O₃, FeOOH, and Fe₃O₄ in dilute sulphuric acid has been directly investigated using graphite paste electrodes containing the oxides. It has been found that these oxides sustain redox reactions at a high positive potential which is stabilised by the presence of ferrous sulphate in the solution and, at saturation, tends to coincidence with the Flade potential. The redox process can be formulated, for example, as Fe₂O₃(its)+2H⁺+2H₂SO₄+2e^?=2FeSO₄s+3H₂O(1) and the potential derived from the free energy change is approximately right. γ-oxides and hydroxyoxides of iron enter into reaction more readily than their α-analogues, and this would be expected on structural grounds.     

Development of iron oxide sorbents for Hg removal from coal derived fuel gas: Sulfidation characteristics of iron oxide sorbents and activity for COS formation during Hg removal

The aim of this study is to develop a process for the removal of Hg⁰ using H₂S over iron oxides sorbents, which will be located just before the wet desulfurization unit and catalytic COS converter of a coal gasification system. It is necessary to understand the reactions between the iron oxide sorbent and other components of the fuel gas such as H₂S, CO, H₂, H₂O, etc. In this study, the sulfidation behavior and activity for COS formation during Hg⁰ removal from coal derived fuel gas over iron oxides prepared by precipitation and supported iron oxide (1 wt% Fe₂O₃/TiO₂) prepared by conventional impregnation were investigated. The iron oxide samples were dried at 110 °C (designated as Fe₂O₃-110) and calcined at 300 and 550 °C (Fe₂O₃-300 and Fe₂O₃-550). The sulfidation behavior of iron oxide sorbents in coal derived fuel gas was investigated by thermo-gravimetric analysis (TGA). COS formation during Hg⁰ removal over iron oxide sorbents was also investigated using a laboratory-scale fixed-bed reactor. It was seen that the Hg⁰ removal activity of the sorbents increased with the decrease of calcinations temperature of iron oxide and extent of sulfidation of the sorbents also increased with the decrease of calcination temperature. The presence of CO suppressed the weight gain of iron oxide due to sulfidation. COS was formed during the Hg⁰ removal experiments over Fe₂O₃-110. However, in the cases of calcined iron oxides (Fe₂O₃-300, Fe₂O₃-550) and 1 wt% Fe₂O₃/TiO₂, formation of COS was not observed but the Hg⁰ removal activity of 1 wt% Fe₂O₃/TiO₂ was high. Both FeS and FeS₂ were active for Hg⁰ removal in coal derived fuel gas without forming any COS.     

Effect of organic acid to enhance the oxidative power of the fenton-like system: Computational and empirical evidences

A Fenton-like system based on the combination of organic acid and hydrogen peroxide over an iron oxide surface was investigated. DFT calculations showed that HCOOH and H₂O₂ interact to produce the pair H₂O₂//HCOOH which leads to the formation of ¹OH more strongly than H₂O₂ alone, upon acceptance of a single electron. Empirical tests using H₂O₂ and HCOOH over iron oxides showed that Fe²⁺ contents and HCOOH enhance degradation of the reactive textile drimaren red dye in agreement with calculations.     

Activated carbon/iron oxide magnetic composites for the adsorption of contaminants in water

In this work the adsorption features of activated carbon and the magnetic properties of iron oxides were combined in a composite to produce magnetic adsorbents. These magnetic particles can be used as adsorbent for a wide range of contaminants in water and can subsequently be removed from the medium by a simple magnetic procedure. Activated carbon/iron oxide magnetic composites were prepared with weight ratios of 2:1, 1.5:1 and 1:1 and characterized by powder XRD, TG, magnetization measurements, chemical analyses, TPR, N₂ adsorption-desorption isotherms, Mössbauer spectroscopy and SEM. The results suggest that the main magnetic phase present is maghemite (γ-Fe₂O₃) with small amounts of magnetite (Fe₃O₄). Magnetization enhancement can be produced by treatment with H₂ at 600 °C to reduce maghemite to magnetite. N₂ adsorption measurements showed that the presence of iron oxides did not significantly affect the surface area or the pore structure of the activated carbon. The adsorption isotherms of volatile organic compounds such as chloroform, phenol, chlorobenzene and drimaren red dye from aqueous solution onto the composites also showed that the presence of iron oxide did not affect the adsorption capacity of the activated carbon.     

Preparation of composite cathode material by using the extracted lead (Pb) of waste lead acid battery for LT-SOFC

The extraction of Pb from the waste lead acid batteries offers the conservation of energy resources and reduction of pollution load in the environment. The recycling of waste lead acid batteries than discarding by conventional methods is the best way. In the present studies, for LT-SOFC, three composite cathode materials (Pb_0.1Fe_0.4Co_0.5O_4-δ, Pb_0.2Fe_0.3Co_0.5O_4-δ and Pb_0.3Fe_0.2Co_0.5O_4-δ) were produced by extracting Pb from the waste lead acid batteries, cobalt nitrate [Co(NO₃)₃.6H₂O] and iron nitrate [Fe(NO₃)₃.9H₂O] using standard solid state reaction method. Thermal stability, morphological and structural characteristics were studied by TGA, SEM and XRD analyses. FTIR spectra were used to investigate the types of metal oxide bonding in the prepared ceramic composite cathode materials. Fuel cell testing and DC four probes were used to investigate electrochemical properties. The measurement of average crystalline size of the composites was found to be in the range of 12–37 nm.Scanning electron microscopy (SEM) images showed that composite materials are porous and suitable to diffuse the gases. The maximum conductivities of 1.6 Scm^?1, 2.05 Scm^?1 and 2.6 Scm^?1 have been obtained for Pb_0.1Fe_0.4Co_0.5O_4-δ, Pb_0.2Fe_0.3Co_0.5O_4-δ and Pb_0.3Fe_0.2Co_0.5O_4-δ, respectively. At 600 °C, the high OCV (0.95V) and the maximum power density (439 mW/cm²) have been achieved using hydrogen as the fuel. Lower value of activation energy (0.36ev) of Pb_0.3Fe_0.2Co_0.5O_4-δ confirms that it is the efficient material to convert electrochemically hydrogen fuel into valuable electricity.     

Enhanced catalytic oxidation via nano Cu0.5Mg0.5Fe2O4 embedded in CNTs for adsorption–reduction of hexavalent chromium

A catalyst consisting of Cu_0.5Mg_0.5Fe₂O₄ (CMF) supported on carbon nanotubes (CNTs) which exhibits great potential as an adsorbent for treating Cr(VI)-contaminated wastewater has been successfully prepared. The ferrite possesses excellent magnetic properties, while CNTs have the advantage of a large surface area. This composite material not only prevents the aggregation of magnetic materials and enhances the exposure of active sites but also effectively solves the recycling problem of CNTs. Our results show that the adsorption capacity of Cu_0.5Mg_0.5Fe₂O₄–carbon nanotubes (CMF-CNTs) for Cr(VI) wastewater (45.60 mg/g) is 1.49 times higher than that of Cu_0.5Mg_0.5Fe₂O₄ (30.48 mg/g). Compared to a single catalyst, CMF-CNTs not only improve the dispersibility of magnetic materials but also exhibit synergistic effects between the composite materials, enhancing the chemical adsorption capacity. After five consecutive adsorption and desorption experiments, the adsorption capacity of CMF-CNTs remains at 88% of its initial value. Furthermore, the study of the catalyst before and after adsorption by XPS reveals that the valence state transition of Fe³⁺/Fe²⁺ and Cu²⁺/Cu⁺ plays a crucial role in the adsorption process. The results of this study demonstrate the potential of using waste materials for effective wastewater treatment and provide insights into the development of new adsorbents for pollutant removal.     

Energy transfer to Eu(III) in the solid‐state low‐density polyethylene–poly(acrylic acid) and low‐density polyethylene–Fe2O3–poly(acrylic acid) matrices

Ion exchange between H⁺ and Eu³⁺ and/or Tb³⁺ was studied in the material modified by in situ sorption and thermal polymerization of acrylic acid in low‐density polyethylene (LDPE–PAA) and in the composite system LDPE–Fe₂O₃–PAA. Fluorescence spectroscopy showed evidence of Eu³⁺ and/or Tb³⁺ ion exchanges in these materials. The matrix LDPE–PAA after Eu(III) ion exchange presented luminescence (excitation 265 nm). This was explained by an energy‐transfer process from the matrix LDPE–PAA to Eu³⁺ ions. The LDPE–PAA matrix after simultaneous Eu³⁺/Tb³⁺ ion exchange exhibited Eu³⁺ and Tb³⁺ ion luminescence (excitation 265 nm), confirming an energy‐transfer process from LDPE–PAA to Eu³⁺ ions in LDPE–PAA–Eu³⁺–Tb³⁺ matrix. Fe₂O₃ in LDPE–Fe₂O₃–PAA quenched the matrix for excitation at 265 nm and no emission at the region 400 nm was observed. The luminescence of Tb³⁺ ions in the matrix LDPE–Fe₂O₃–PAA–Tb³⁺ (excitation 265 nm) was partially quenched by Fe₂O₃. However, a weak emission of Eu³⁺ ions was observed (excitation 265 nm) in the matrix LDPE–Fe₂O₃–PAA after simultaneous Eu³⁺ and Tb³⁺ ion exchanges, suggesting an energy transfer from Tb³⁺ to Eu³⁺ ions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 919–931, 2000     

Study on an iron–manganese Fischer–Tropsch synthesis catalyst prepared from ferrous sulfate

A systematic study was undertaken to investigate the effects of the initial oxidation degree of iron on the bulk phase composition and reduction/carburization behaviors of a Fe–Mn–K/SiO₂ catalyst prepared from ferrous sulfate. The catalyst samples were characterized by powder X-ray diffraction (XRD), Mössbauer spectroscopy, X-ray photoelectron spectroscopy (XPS) and H₂ (or CO) temperature-programmed reduction (TPR). The Fischer–Tropsch synthesis (FTS) performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor (CSTR). The characterization results indicated that the fresh catalysts are mainly composed of α-Fe₂O₃ and Fe₃O₄, and the crystallite size of iron oxides is decreased with the increase of the initial oxidation degree of iron. The catalyst with high content of α-Fe₂O₃ in its as-prepared state has high content of iron carbides after being reduced in syngas. However, the catalyst with high content of Fe₃O₄ in its as-prepared state cannot be easily carburized in CO and syngas. FTS reaction study indicates that Fe-05 (Fe³⁺/Fe_total = 1.0) has the highest CO conversion, whereas Fe-03 (Fe³⁺/Fe_total = 0.55) has the lowest activity. The catalyst with high CO conversion has a high selectivity to gaseous hydrocarbons (C₁–C₄) and low selectivity to heavy hydrocarbons (C₅₊).     

Effect of Fe2+ and Fe0 Applied Photo‐Fenton Processes on Sludge Disintegration

The disintegration of waste active sludge was investigated by photo‐Fenton processes. A batch study was conducted to evaluate parameters, such as Fe²⁺ and Fe⁰ ions and H₂O₂, governing the activated sludge integration by the photo‐Fenton process. Under optimum conditions, the concentration of soluble chemical oxygen demand (SCOD) with the classical Fenton process (CFP) increased very rapidly in the first five minutes due to the sufficient presence of reaction components in the medium, and then the rate of increase declined. In the modified Fenton process (FTP), the SCOD concentration increased more slowly as metallic iron powder must first be dissolved. The photo‐Fenton process proved to be a feasible and efficient process for the disintegration of waste sludge.     

Ferrous-Ferric Ratio and CEC Changes on Deferration of Weathered Micaceous Vermiculite

Ferrous iron in the layers increased 2-fold or more on deferration of coarser fractions of micaceous vermiculite naturally weathered from biotite (Colorado and Transvaal sources). The ferric iron content of the layers was decreased by the deferration treatment but the original content was restored by subsequent H₂O₂ treatment. Sesquioxide coatings on micaceous vermiculite from Colorado, examined electron microscopically, were composed predominantly of Fe₂O₃ (80 to 85 percent), along with Al₂O₂ and SiO₂. The CEC increased from 64 to 95 meq per 100 g in the fraction coarser than 1000 microns and 50 to 64 meq per 100 g in the fraction 2–0.2, microns in diameter, as a result of removal by deferration of positively charged sesquioxide coating which had originally blocked a portion of the CEC. Although treatment with H₂O₂ after deferration restored the Fe³⁺ content to approximately the original value, the CEC was not affected probably because of deprotonation OH^? → O^2? + H⁺ occurring simultaneous with Fe²⁺ → Fe³⁺.     

Kinetic studies on the reactions involved in the hot gas desulfurization using a regenerable iron oxide sorbent—II: Reactions of iron sulfide with oxygen and sulfur dioxide

In the hot gas desulfurization process using iron oxide sorbent, the regeneration of the sulfided iron oxide sorbent consists of two reactions: the oxidation of iron sulfide with air, and its reaction with the sulfur dioxide formed during the air oxidation. This part describes the kinetic studies on the reactions of iron sulfide (formed by the reactions of Fe₂O₃ with H₂CO mixture and subsequendy with H₂S) with oxygen and sulfur dioxide. The experimental and analysis procedures used are similar to those outlined in Part I of this paper.The activation energies for the oxygen and the sulfur dioxide reactions are found to be 15.63 and 17.5 kcal/mol, respectively. Notably, the product oxides formed in the two cases are different. With air, the reaction is fast and the final product is Fe₂O₃, whereas with SO₂, the major product is Fe₃O₄, which slowly oxidizes to Fe₂O₃ in a secondary step. Also, in the latter reaction elemental sulfur is formed.     

The SPASIBA Force Field for Studying Iron-Tannins Interactions: Application to Fe3+/Fe2+ Catechol Complexes

The SPASIBA force field parameters have been obtained for Fe³⁺/Fe²⁺-Oxygen interactions occuring between non-heminic iron and hydroxyl groups of polyphenols found in tannins. These parameters were derived from normal modes analyses based on quantum chemical calculations using the Density Functional Theory (DFT). Four models involving complexation of iron with water ([Fe(H₂O)₆]³⁺, [Fe(H₂O)₆]²⁺) and with cathechol molecules ([Fe(cat)₂(H₂O)₂]⁻¹, [Fe(cat)₂(H₂O)₂]⁻²) were studied using the Density Functional Theory and the B3LYP hybrid functional under high spin states of iron.     

Electrocatalyst materials for fuel cells based on the polyoxometalates—K7 or H7[(P2W17O61)Fe(H2O)] and Na12 or H12[(P2W15O56)2Fe4(H2O)2]

Free acids of the iron substituted heteropoly acids (HPA), H₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (HFe1) and H₁₈[(P₂W₁₅O₅₆)₂Fe^III₂(H₂O)₂] (HFe2) were prepared from the salts K₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (KFe1) and Na₁₂[(P₂W₁₅O₅₆)₂Fe^III₄(H₂O)₂] (NaFe4), respectively. The iron-substituted HPA were adsorbed on to XC-72 carbon based GDLs to form HPA doped GDEs after water washing with HPA loadings of ca. 1 μmol. The HPA was detected throughout the GDL by EDX. Solution electrochemistry of the free acids are reported for the first time in sulfate buffer, pH 1-3. The hydrogen oxidation reaction was catalyzed by KFe1 at 0.33 V, with an exchange current density of 38 mA/cm². Moderate activity for the oxygen reduction reaction was observed for the iron substituted HPA, which was dramatically improved by selectively removing oxygen atoms from the HPA by cycling the fuel cell cathode under N₂ followed by reoxidation to give a restructured oxide catalyst. The nanostructured oxide achieved an OCV of 0.7 V with a Tafel slope of 115 mV/decade. Cycling the same catalysts in oxygen resulted in an improved catalyst/ionomer/carbon configuration with a slightly higher Tafel slope, 128 mV/decade but a respectable current density of 100 mA/cm² at 0.2 V.     

Modeling dye degradation kinetic using dark- and photo-Fenton type processes

Dark- and photo-Fenton type processes, Fe²⁺/H₂O₂, Fe³⁺/H₂O₂, Fe⁰/H₂O₂, UV/Fe²⁺/H₂O₂, UV/Fe³⁺/H₂O₂ and UV/Fe⁰/H₂O₂, were applied for the treatment of model colored wastewater containing two reactive dyes, C.I. Reactive Blue 49 and C.I. Reactive Blue 137, and degradation kinetics were compared. Dye degradation was monitored by the means of UV/VIS, adsorbable organic halides (AOX) and total organic carbon (TOC) analysis, thus determining decolorization and dechlorination of triazine structure, as well as mineralization of model colored wastewater. Both dark- and photo-Fenton type processes were proven to be very efficient for color removal; ≥98% was achieved in all cases. Significant improvements in the mineralization of studied dyes were achieved by the assistance of UV light, as it was expected. It was demonstrated that the degradation kinetic of applied dyes depended on the presence of UV light, as well as type of iron catalyst and dye structure. On bases of the obtained experimental results, the mathematical models were developed describing dye degradation kinetics in all studied systems. Since UV light was used in order to enhance the efficiency of dark-Fenton type processes, mathematical model describing dye degradation by UV photolysis providing the values of quantum yields for each of the dye was developed and incorporated in model for photo-Fenton type processes. A sensitivity analysis for the evaluation of importance of each reaction used in mathematical models was also performed.     

Recyclage d'un déchet,une boue rouge,comme catalyseur pour l'élimination des composés organiques volatils

The catalytic potential of a red mud, a waste from alumina production, was evaluated for the oxidation of VOC, in particular toluene. When dried, it consists mainly of Al(OH)₃ and Fe₂O₃. It was found that red mud calcination under an air stream at 500 °C leads to the formation of Al₂O₃ and Fe₂O₃, two oxides that are active and CO₂ selective in the toluene oxidation reaction. The red mud activity can be correlated directly to the amount of iron in the sampling. Indeed, the chemical reaction specific rate (by gram of Fe₂O₃) in presence of red mud is similar to that observed in presence of a pure Fe₂O₃ iron oxide.     

Characterization and conversion determination of stable PEDOT latex nanoparticles synthesized by emulsion polymerization

In this research, poly(3,4-ethylenedioxythiophene) (PEDOT) latex nanoparticles with good colloidal stability were prepared by emulsion polymerization and the conversions of EDOT were determined. Two kinds of oxidants, Iron(III) p-toluenesulfonate Fe(OTs)₃ and hydrogen peroxide H₂O₂, were introduced to decrease the use of iron salt and therefore reduce the particle coagulation. The ferrous ions (Fe²⁺) produced during the polymerization would be re-oxidized back to the reactive ferric ions (Fe³⁺) with the help of H₂O₂. This cyclic oxidation-reduction process resulted in the sustained regeneration of Fe³⁺ ions and led to a higher conversion. A dark blue PEDOT latex with long-term dispersion stability was obtained when Fe(OTs)₃ and H₂O₂ were added in sequence. The results obtained from dynamic light scattering and TEM measurements showed that the sizes of nanoparticles were around 100 nm. To determine the conversion of EDOT, two methods (gravimetric analysis and UV-visible method) were used and compared. For the first time, the UV-visible method was established to quantitatively determine the conversion of EDOT monomer. From the measurement, the conversion of EDOT in this system was determined as 74-75%. The PEDOT film prepared by drying the latex solution had conductivity up to 6.3 S/cm.     

Formation of stable passive film on stainless steel by electrochemical deposition of polypyrrole

Stable passive film has been formed on 304 stainless steel during the electrochemical deposition of polypyrrole (PPy) from sulfuric acid solution. The stability of passive film under PPy increases with aging in H₂SO₄ and this film has much higher resistance to pitting than that formed by anodic polarization under the same condition of aging. XPS studies indicate that the content of chromium components in the oxides under PPy layer is about twice that of the anodically formed passive film with larger value of the ratio Cr₂O₃/Cr(OH)₃. Higher content of iron with a ratio of Fe²⁺/Fe³⁺ more than unity is also observed with a considerable lower hydration and sulfate content in the oxides under PPy layer. It is suggested that sulfate ion is consumed as a dopant in the formation of PPy film and the oxidation of stainless steel is achieved under the environment of lower concentration of water and sulfate molecules. This may result in the enhancement of formation of corrosion-resisting oxides rather than hydroxides and sulfates.