Electrochemical aspects of black chromium electrodeposition from 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid

The electrochemical behaviour of trivalent chromium (Cr³⁺) in 1-butyl-3-methylimidazolium tetrafluoroborate [BMIm][BF₄] ionic liquid solutions was studied by cyclic voltammetry and chronoamperometry. The reduction of Cr³⁺ occurs in two steps, Cr³⁺ to Cr²⁺ and Cr²⁺ to Cr⁰, respectively. The first step is quasi-reversible with a diffusion coefficient of Cr³⁺ in solution of 3.13 × 10⁻⁸ cm² s⁻¹ at 303 K and 25.8 × 10⁻⁸ cm² s⁻¹ at 358 K, estimated from cyclic voltammetry data.Black chromium films were electrodeposited on copper, stainless steel and carbon steel substrates at a constant potential of −1.5 V vs Pt quasi-reference electrode. The films consist of aggregates of nanosized particles. The coatings in the as-deposited condition present an amorphous structure but after annealing for 4 h, a nanocrystalline Cr₂O₃ phase is formed, with an average crystallite size of 17 nm.     

Electrochemical synthesis of Cr(II) at carbon electrodes in acidic aqueous solutions

The electrochemical synthesis of Cr(II) has been investigated on a vitreous carbon rotating disc electrode and a graphite felt electrode using cyclic voltammetry, impedance spectroscopy and chronoamperometry. The results show that in 0.1 M Cr(III) + 0.5 M sulphuric acid and in 0.1 M Cr(III) + 1 M hydrochloric acid over an electrode potential range of –0.8 to 0.8 V vs SCE, the electrochemical reaction at carbon electrodes is essentially a surface process of proton adsorption and desorption, without significant hydrogen evolution and chromium(II) formation. At electrode potentials more negative than –0.8 V vs SCE, both hydrogen evolution and chromium(II) formation occurred simultaneously. At electrode potentials –0.8 to –1.2 V vs SCE, the electrochemical reduction of Cr(III) on carbon electrodes is controlled mainly by charge transfer rather than mass transport. Measurements on vitreous carbon and graphite felt electrodes in 1 M HCl, with and without 0.1 M CrCl₃, allowed the exchange current density and Tafel slope for hydrogen evolution, and for the reduction of Cr(III) to Cr(II), to be determined. The chromium(III) reduction on vitreous carbon and graphite electrodes can be predicted by the extended high field approximation of the Butler–Volmer equation, with a term reflecting the conversion rate of Cr(III) to Cr(II).     

Electrooxidation of stainless steel AISI 304 in carbonate aqueous solution at pH 8

The electrochemical behaviour of stainless steel AISI 304 (SS304) has been investigated in deaerated 0.1–1 m NaHCO₃ solutions at pH 8 using a rotating disc electrode. The polarization curves are characterized by a broad range of passivity at low potentials (–0.8 to 0.3 V), a depassivation region at 0.4 V vs SCE and, at high potentials (0.5 to 0.85 V), a passive region before oxygen evolution. In the low potential range, the SS304 electrode behaves like a Cr-rich metallic phase, and the dissolution of Fe²⁺ ions into the solution is hindered by the formation of a Cr₂O₃ layer. As the potential reaches 0.4V, the oxidation-dissolution of Cr(iii) oxide/hydroxide to CrO₄ ² ions occurs, with the participation of bicarbonate/carbonate as a catalyst in the dissolution reaction. Since the chromium oxide/hydroxide dissolution and subsequent surface enrichment of iron oxides occur, the applied potential, exposure time and oxidation charge have a considerable effect on the passive film properties. At high potentials, the presence of a passive film of iron oxides/hydroxides or oxyhydroxides plays a key role in the SS304 passivity with the presence of Fe(vi) species incorporated or adsorbed into the passive films. Colouration of the SS304 surface is observed in the second passive region. A film of a uniform gold colour formed on SS304, mild steel 1024 and iron in carbonate and borate solutions at pH 8. The colour of the electrode surfaces remain unchanged in air and in solutions at positive potential but it disappears at open-circuit potential or is easily reduced in the first negative-going potential scan.     

In situ investigation of active sites in zirconia-supported chromium oxide catalysts during the aromatization of n-octane

Supported chromium oxide catalysts containing 0.5 and 4.0 wt% Cr, respectively, on a 7 wt% La₂O₃/ZrO₂ carrier were studied by in situ EPR equipped with on-line GC during the catalyst pretreatment in flowing H₂ and the aromatization of n-octane in the range 293<T<823 K. Active catalysts contain almost exclusively Cr³⁺ in the form of Cr₂O₃ clusters and isolated, coordinatively unsaturated Cr³⁺ species on the surface. The latter appear to be less sensitive to poisoning by coke deposition and govern residual catalytic activity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electrochemical formation and control of chromium nitride films in molten LiCl-KCl-Li3N systems

Electrochemical formation and control of chromium nitride films have been investigated in molten LiCl-KCl-Li₃N systems at 723 K. Chromium nitride films were obtained by means of potentiostatic electrolysis of chromium electrodes in the melts. From XPS and XRD analyses, it was confirmed that all obtained films consisted of Cr₂N and CrN, and the composition of each nitride layer was effected by the applied potential value. For instance, a nitride layer consists mostly of Cr₂N on a chromium specimen after potentiostatic electrolysis at 1.0 V (vs. Li⁺/Li), and it consists mostly of CrN at 1.5 V. At the potential range from 1.0-1.5 V, the ratio of CrN-Cr₂N in the nitride layer increases, as the applied potential is more positive. Furthermore, the thickness of the nitride layer increases with increasing the electrolysis time. The obtained results suggest that compositions and thickness of nitride films can be controled by electrolytic conditions, e.g. applied potential and electrolysis time.     

Investigation of a transparent chromate (III) passive film on electroless Ni–P coating by XPS and electrochemical methods

A transparent passive film on electroless nickel phosphorus coating (ENPC) was obtained in a chromate (Cr³⁺) bath. An ENPC sample passivated in a Cr⁶⁺-containing bath was used for comparison. The corrosion properties were tested by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). SEM, XPS, and EDX were employed to analyze the chemical composition and surface morphology of the films. SEM results indicate that the passive film is too thin to be observed by SEM. The potentiodynamic polarization tests show that the corrosion currents of the two passivated samples are only about 1/25 of the un-passivated coating. The XPS analysis illustrate that the Cr⁶⁺-treated film comprises Cr, Ni and O, while the Cr³⁺-treated film is made up of Cr, C, O, Ni, P and N. High-resolution XPS analysis show that, both in Cr⁶⁺-treated and Cr³⁺-treated films, element Cr is only in the form of trivalent compounds, no hexavalent chromium existing. By XPSpeak analyzing, trivalent chromium compounds on the two treated surfaces were fitted as Cr(OH)₃ and Cr₂O₃. However, for the Cr³⁺ and Cr⁶⁺ passivation routes, the Cr(OH)₃ and Cr₂O₃ contents in passive films are widely divergent.     

Enhancement of electrocatalytic properties of carbonized polyaniline nanoparticles upon a hydrothermal treatment in alkaline medium

The electrocatalytic activity of carbonized polyaniline nanostructures (Carb-nanoPANI) towards oxygen reduction reaction (ORR), estimated in 0.1 mol dm⁻³ KOH solution, was significantly improved upon a hydrothermal treatment in 1 mol dm⁻³ KOH solution. Namely, the onset of ORR was shifted by ∼70 mV to more positive potentials, and the number of electrons consumed per O₂ molecule was enhanced in comparison to the original material. The number of electrons involved in ORR depended on loading, and with a loading of 0.5 mg cm⁻², for the potentials lower than −0.5 V vs SCE, the number of electrons approached 4. For this material, high stability of electrochemical behavior and resistance to the poisoning by ethanol was evidenced by potentiodynamic cycling.     

Effect of support structure on the activity of Cr/nanosilica catalysts and the morphology of prepared polyethylene

Phillips‐type catalysts are responsible for the commercial production of more than one‐third of all polyethylene sold worldwide. Many types of chromium‐based catalysts are used in the Phillips polymerization process. Ordered mesoporous silica structures were synthesized using various surfactant species. Chromium nitrate nonahydrate (Cr(NO₃)₃·9H₂O) complex was grafted onto the surface of pure silica and was used for ethylene polymerization. The materials were characterized using X‐ray diffraction, nitrogen adsorption‐desorption, inductively coupled plasma optical emission spectroscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy. In the as‐synthesized materials, Cr³⁺ is present as a surface species in pseudo‐octahedral coordination. After calcination, Cr³⁺ is almost completely oxidized to Cr⁶⁺, which is anchored onto the surface in various oxidative states. The catalyst polymerization activity is dependent on the chromium loading, the pre‐calcination temperature and the support properties. In particular, the chromium catalyst prepared using spherical SBA‐15 is more active than the other catalysts investigated. Porous and nano‐fibrous polyethylene samples were prepared using various silica‐supported chromium catalytic systems. Differential scanning calorimetry results show that the melting point of samples produced with the SBA‐15‐supported catalyst is higher than that of samples produced with Cr/SiO₂ under the same conditions, which could be related to the existence of an extended‐chain structure. Copyright © 2010 Society of Chemical Industry     

Performance of H‐ZSM‐5‐supported bimetallic catalysts for the combustion of polluting volatile organic compounds in air

The performance of H‐ZSM‐5‐supported bimetallic catalysts with chromium as the base metal in the combustion of ethyl acetate and benzene is reported. A reactor operated from 100 to 500 °C at a gas hourly space velocity (GHSV) of 32 000 h^?1 was used for study of the activity. A combination of 1.0 wt% chromium and 0.5 wt% copper yielded a catalyst (Cr_1.0Cu_0.5/Z) with improved conversion and carbon dioxide yield. Cr₂O₃ (Cr³⁺) and CuO (Cu²⁺) were the predominant metal species in the catalyst. In agreement with the Mars–van Krevelen model, improved reducibility of Cr³⁺ in the presence of Cu²⁺ led to an improvement in activity. The copper content in Cr_1.0Cu_0.5/Z also favored the formation of deep combustion products. Condensation and subsequent growth of coke precursors in the catalyst pores led to the formation of a softer and less aromatic coke fraction while dehydrogenation activity on acid sites formed a harder and more aromatic coke fraction. The use of Cr_1.0Cu_0.5/Z favored the formation of lower molecular weight intermediates, leading to reduction in formation of softer coke. Copyright © 2005 Society of Chemical Industry     

Catalytic nitroxidation of para-xylene over chromium oxide based catalysts

The synthesis of para-tolunitrile (PTN) and terephthalonitrile (TPN) by reacting nitrogen monoxide with para-xylene was studied in presence of three chromium oxide catalysts. The Cr₂O₃—Al₂O₃ catalyst was prepared under the form of aerogel or xerogel and shows excellent selectivities in nitriles along with good stability. However, the unsupported Cr₂O₃ catalyst showed much less performance and, in particular, produced no TPN. The beneficial action of alumina was explained in terms of stabilization of the Cr⁵⁺ species. Kinetic results seemed to indicate a redox-type mechanism of the reaction. Moreover the PTN was shown to be an intermediate in TPN formation.     

Optimization of chromium removal by the chromium resistant mutant of the cyanobacterium Anacystis nidulans in a continuous flow bioreactor

BACKGROUND: Chromium removal potential of the cyanobacterium Anacystis nidulans and its chromium resistant strain Cr^rI8 has been optimized. Optimized parameters include biomass load, pH, temperature and dilution rate of the bioreactor. RESULTS: Results show that chromium resistant strain has high EC₅₀ dose for chromium compared to wild strain. Chromium removal potential of both strains is strongly influenced by various factors. Optimized conditions in batch system included pH 6.5, temperature 28 °C, biomass load 150 µg protein mL^?1 for 30 µmol L^?1 Cr⁶⁺ solution. In continuous flow bioreactor at optimum pH (6.5) and temperature (28 °C) at a fixed biomass of 10 mg protein and 30 µmol L^?1 Cr⁶⁺, metal removal efficiency varied with dilution rate. For A. nidulans continuous flow bioreactor, optimum dilution rate was 0.076 h^?1 (64.6 per cent metal removal) while for Cr^rI8 it was 0.152 h^?1 (85.8 per cent metal removal). Operative time of the Cr^rI8 bioreactor was also more (85 h) compared to A. nidulans bioreactor (45 h). CONCLUSION: Under optimized conditions resistant strain Cr^rI8 removed more Cr⁶⁺ compared to A. nidulans and thus has the potential to be exploited for Cr⁶⁺ removal from industrial effluents at large scale. Copyright © 2007 Society of Chemical Industry     

Effect of heat treatment on microstructure and properties of powder immersion reaction assisted chromium carbide coatings prepared on Q235 steel

In this work, powder immersion reaction assisted (PIRAC) chromium carbide coatings prepared on Q235 steel at 800 and 900°C were heat-treated in vacuum at 900 and 1000°C, respectively. The effects of heat treatments on the phase compositions, microhardness, and oxidation behavior in the air of the as-prepared PIRAC chromium carbide coatings were investigated. Under further heat treatments, Cr₂₃C₆ in the chromium carbide coatings was carburized due to the diffusion of carbon and transformed into Cr₃C₂ and Cr₇C₃ and subsequently, the microhardness of the coatings increased. The higher the heat treatment temperature, the higher the amount of Cr₃C₂ and Cr₇C₃ and the greater microhardness of the coatings. The as-prepared and heat-treated chromium carbide coatings experienced similar parabolic oxidation weight gains with time. Further heat treatments led to the oxidation-induced weight gain and the parabolic oxidation rate constant decreased.     

Influence des ions chlorure sur la reduction electrochimique du chrome(VI)

Electrochemical reduction of chromium(VI) was performed in both chloride and sulfate media, introducing potassium dichromate in a carbon paste electrode with a conducting binder. For acid concentrations lower than 0.2 M both in the bulk and the binder, the voltammetric curves are identical in sulfuric or hydrochloric media, and may be interpreted as the result of a blocking effect due to Cr(OH)₃ formation at the carbon particles' surface, because of a lack of protons. For lower pH values, in sulfuric medium, Cr₂O²⁻₇ ions are reduced irreversibly into Cr³⁺ ions, but in hydrochloric medium, chromium(VI) exists under two different ions: Cr₂O²⁻₇ and CrO₃Cl⁻. The reduction of trioxochlorochromate ions CrO₃Cl⁻ into Cr³⁺ ions is found to be reversible. Attempts to measure the standard potential in 1 M HCl lead to a value close to 0.43 V/sce.     

Erosive and corrosive wear performance and characterization studies of plasma-sprayed WC/Cr3C2 coating on SS316

Plasma spray coating with ceramic carbide is a promising approach for improving the surface quality of the materials. In this work, the effectiveness of tungsten carbide (WC), chromium carbide (Cr₃C₂), and the composite coating of the two powders in the weight ratio of 50:50 were investigated. In the erosion test, aluminum oxide (Al₂O₃) particles were combined with a high-speed air-jet and impinged at 90° on the top surface of the material. Electrochemical polarization and electrochemical impedance spectroscopy studies were conducted with a 3.5 wt.% of sodium chloride (NaCl) solution as the electrolyte. Using a scanning electron microscope, the surface morphology of powders and coatings, as well as the mechanisms of erosion and corrosion, were studied. Energy-dispersive X-ray analysis and X-ray diffractometry were used to reveal the composition and elemental distribution of the feedstock powders and coatings. Because of the presence of hard phases, the composite coating shows the highest average microhardness of 1350.2 HV. The composite coating exhibits improved erosive wear resistance with an increase in erodent exposure time. The Cr₃C₂ coating has a reduced corrosion current density of 1.404 × 10⁻⁵ mA/cm² and a higher charge transfer resistance of 2086.75 Ω cm² due to passivation.     

Electrodeposition of High-quality Polycarbazole Films in Composite Electrolytes of Boron Trifluoride Diethyl Etherate and Ethyl Ether

High-quality polycarbazole (PCZ) films were synthesized electrochemically by direct oxidation of carbazole in boron trifluoride diethyl etherate (BFEE) containing vol. 20% ethyl ether (EE). The oxidation potential of carbazole in this medium was measured to be only 0.90 V vs. SCE, which was lower than that determined in acetonitrile containing 0.1 mol l⁻¹ Bu₄NBF₄ (1.35 V vs. SCE). PCZ films obtained from this medium showed better electrochemical behavior, better thermal stability with conductivity of 7.5 × 10⁻³ S cm⁻¹ being one order of magnitude higher than those reported previously, indicating that BFEE/EE was a better medium than acetonitrile for the electrosyntheses of PCZ films. As-formed PCZ films can be partly dissolved in acetone, acetonitrile and tetrahydrofuran. Spectral analysis provided evidence for the existence of the conjugated structure of the PCZ chain. Fluorescent spectra indicate that electrosynthesized PCZ is an ideal blue light emitter.     

Preparation and characterization of Bi-doped antimony selenide thin films by electrodeposition

Bi-doped antimony selenide (Sb_2−xBi_xSe₃) thin films have been prepared by potentiostatical electrodeposition and post annealing treatment. Cyclic voltammetry (CV) was used to investigate the electrochemical behaviors of electrodeposition. The suitable deposition potential for film preparation was determined to be about −0.40 V vs. SCE combining with CV, energy dispersive X-ray spectroscopy (EDS), environmental scanning electron microscope (ESEM) studies. After annealing, film shows improved crystallinity and a basic orthorhombic Sb₂Se₃ structure but having a larger d-spacing due to the substitution of Bi for Sb in Sb₂Se₃ lattice. The annealed film exhibits an absorption coefficient of larger than 10⁵ cm⁻¹ in the visible region, an direct optical band gap of 1.12 ± 0.01 eV, the n-type conductivity, an carrier concentration of 1.1 × 10¹⁹ cm⁻³ and an flat band potential of −0.40 ± 0.03 V vs. SCE.     

Hexacyanoferrate ion adsorbed on propylpyridiniumsilsesquioxane polymer film-coated SiO2/Al2O3: use in an electrochemical oxidation study of cysteine

Hexacyanoferrate ion, [Fe(CN)₆]⁴⁻, was immobilized by an ion-exchange reaction on the propylpyridiniumsilsesquioxane chloride polymer thin-film-coated SiO₂/Al₂O₃ surface. The amount of [Fe(CN)₆]⁴⁻ immobilized was 0.22 mmol g⁻¹ with a surface coverage of 9.6×10⁻⁶ mmol cm⁻². A carbon paste electrode made with this material was prepared and its electrochemical properties studied. The electrode presented two well-defined redox peaks with midpoint potentials, E_m, of 0.152 V vs SCE. This potential was not significantly affected by pH changes between 2 and 9.5. The electrode showed much reproducible responses and was successfully used to study the electrochemical oxidation of cysteine.     

Influence of the Fuel Used in the Microwave Synthesis of Cr2O3

The synthesis and physico-chemical characterization of chromium oxide (Cr₂O₃) is reported. Samples were prepared by a novel microwave technique using two different fuels, i.e., tetraformaltrisazzine (TFTA) and urea. The physical characterization of the synthesized chromium oxides was achieved using XRD, IR, Raman, BET surface area and pore size distribution (PSD) techniques. The XRD and IR and Raman spectroscopy studies reveal that crystalline Cr₂O₃ is the only phase formed. The XRD, surface area and particle size analysis reveal that the samples prepared using TFTA as the fuel possess a larger surface area, smaller crystalline size, smaller particle size and larger pore diameter. Both samples were calcined at 600°C for 6 h so that they could be used for the catalytic oxidation of LPG. Catalytic runs on the Cr₂O₃ samples revealed that the two samples possess different activity and selectivity. The Cr₂O₃ sample prepared by using TFTA as the fuel gave rise to more dehydrogenation and cracking compared to the sample prepared by using urea as the fuel, which gave more combustion products.     

Properties of the Cr2O3/MgF2 system — catalytical aspect

The influence of Cr₂O₃ on properties of the Cr₂O₃/MgF₂ catalysts obtained by impregnation and precipitation-deposition is described. The IR technique enabled monitoring of changes in the structure of the MgF₂ surface after introducing chromium ions. Tetrahedral chromium complexes as well as structures of Cr₃O₃ type were observed. The deposited species generated the Lewis and BrØnsted acidity which in turn was responsible for the catalytic activity in the reactions of 2-propanol decomposition, butène double bond isomerization, cumene cracking, dehydrogenation of cyclohexane and decomposition of methyl alcohol.     

Potentiometric study of the interaction of Cr and O ions in fused NaCl-2CsCl eutectic

The physical and chemical properties of chromium chlorides have been studied in fused NaCl-2CsCl eutectic at the temperature range 843-1008 K using an electrochemical cell containing a platinum-oxygen electrode with solid electrolyte membrane, which was used as pO²⁻ indicator electrode. The concentration of oxygen ions in the solution was modifying by dropping the calculated amount of BaO. Titration of Cr³⁺ chlorocomplex by O²⁻ ions demonstrated the precipitation of CrOCl and Cr₂O₃. The solubility constants of these compounds were calculated. E-pO²⁻ and three-dimensional E-pO²⁻-T type diagrams, which summarized the properties of chromium species in the melt, were determined.