Electrochemical incineration of oxalic acid: Reactivity and engineering parameters

Mass transfer measurements were carried out to test a disk-shaped parallel-plate electrochemical cell, based on a new design. The impinging-jet-cell concept, confined between parallel plates, was adapted to a configuration with one central inlet and several peripheral exit sections, leading to more effective hydrodynamics within the cell. Measurements of mass transfer coefficient were performed using the limiting diffusion current technique based on ferro-cyanide ion oxidation, and overall mass transfer coefficients were correlated to Reynolds numbers ranging from 30 to 200.  A comparison with literature on similar devices showed higher mass transfer coefficients can be obtained in the cell described in the present work. From the mass transfer standpoint, this type of cell could be a valuable tool in electrochemical wastewater treatment applications.  The electrochemical oxidation of oxalic acid was tested at different anode materials (Pb/PbO₂, boron-doped diamond, Ti/Pt and Ti/IrO₂–Ta₂O₅), showing that the new cell design enables limitations usually encountered with conventional batch cells to be overcome. However, the nature of the anode material remains an important parameter for the elimination of organic substrates.     

Kinetic modelling of the electrochemical mineralization of organic pollutants for wastewater treatment

The electrochemical mineralization of organic pollutants is a new technology for treatment of dilute wastewater (COD < 5 g L⁻¹). In this method, use of the electrical energy can produce complete oxidation of pollutants on high oxidation power anodes. An ideal anode for this type of treatment is a boron-doped diamond electrode (BDD) characterized by a high reactivity towards oxidation of organics. In the present work kinetic aspects of organic mineralization is discussed. The proposed theoretical kinetic model on boron-doped diamond anodes is in excellent agreement with experimental results. In addition economic aspects of electrochemical organic mineralization are reported.     

The effect of CVD-diamond film thickness on the electrochemical properties of synthetic diamond thin-film electrodes

The electrochemical behavior of polycrystalline diamond films of different thickness (0.5–7 μm), grown by hot-filament CVD method, was studied by electrochemical impedance spectroscopy and cyclic voltammetry. The differential capacitance, background current, and potential window were measured in supporting electrolyte solution; the electrochemical kinetics, in [Fe(CN)₆]^3−/4− model redox system. With the increasing of the films thickness, the crystallite size increased; both the differential capacitance and background current in the indifferent electrolyte, as well as the transfer coefficients in the redox system, decreased; thus, the diamond electrode becomes as if less reversible. The effect of the films’ thickness is reduced to that of nondiamond (amorphous) carbon contribution from intercrystalline boundaries on the electrochemical behavior of the polycrystalline diamond electrodes.     

Electrochemical membrane reactor for the reduction of carbondioxide to formate

An electrochemical reactor with anode and cathode chambers separated by a composite perfluoro polymer cation exchange membrane was designed, fabricated and used for the reduction of dissolved carbon dioxide under ambient conditions to formate. The flow reactor enhanced the mass transfer of carbon dioxide compared to the batch reactor and maximum current efficiency of 93% for formate formation was obtained. A formate concentration of 1.5 × 10⁻² mol dm⁻³ was obtained. Experiments were conducted using two different perfluoro polymer membranes – Nafion 961 and Nafion 430. Optimum values of flow rate and current density were evaluated for the energy efficient formation of formate in aqueous phosphate buffer solutions.     

Characterization of the performance and failure mechanisms of boron-doped ultrananocrystalline diamond electrodes

This research investigated the anodic stability of boron-doped ultrananocrystalline diamond (BD-UNCD) film electrodes on a variety of substrates (Si, Ta, Nb, W, and Ti) at a current density of 1 A cm⁻². At an applied charge of 100 A h cm⁻², measurable BD-UNCD film wear was not observed using SEM cross-sectional measurements. However, anodic treatment of the electrodes resulted in surface oxidation and film delamination, which caused substantial changes to the electrochemical properties of the electrodes. The substrate roughness, substrate electroactivity, and compactness of the substrate oxide were key parameters that affected film adhesion, and the primary mechanism of electrode failure was delamination of the BD-UNCD film. Substrate materials whose oxides had a larger coefficient of thermal expansion relative to the reduced metal substrates resulted in film delamination. The approximate substrate stability followed the order of: Ta > Si > Nb > W ≫ Ti.     

On the activation and physical degradation of boron-doped diamond surfaces brought on by cathodic pretreatments

The electrochemical activation and physical degradation of boron-doped diamond (BDD) electrodes with different boron doping levels after repeated cathodic pretreatments are reported. Galvanostatic cathodic pretreatment passing up to −14000 C cm⁻² in steps of −600 C cm⁻² using −1 A cm⁻² caused significant physical degradation of the BDD surface, with film detachment in some areas. Because of this degradation, a great increase in the electrochemically active area was observed in Tafel plots for the hydrogen evolution reaction (HER) in acid media. The minimum cathodic pretreatment needed for the electrochemical activation of the BDD electrodes without producing any observable physical degradation on the BDD surfaces was determined using electrochemical impedance spectroscopy (EIS) measurements and cyclic voltammetry: −9 C cm⁻², passed at −1 A cm⁻². This optimized cathodic pretreatment can be safely used when electrochemical experiments are carried out on BDD electrodes with doping levels in the range between 800 and 8000 ppm.     

Anodic oxidation of organic pollutants on a Ti/SnO<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>4</Subscript> anode

A Ti/SnO₂–Sb₂O₄ electrode was prepared by alternate Sn and Sb electrodepositions using the thermo-electrochemical method. The chemical, electrochemical, and structural characterization of the electrode was performed and it was tested in the anodic oxidation of several pollutants, phenol, ibuprofen, acid orange 7 (AO7), and diclofenac, all in aqueous 0.035 M Na₂SO₄ solutions at current densities of 10 and 20 mA cm⁻². After the 24 h assay, removal of chemical oxygen demand, total organic carbon (TOC) and absorbance were very high, especially at the higher current density. TOC removals presented the lowest value. However, after 24 h at 20 mA cm⁻², TOC removals were: phenol—94%; ibuprofen—83%; AO7—88%; and diclofenac—73%. Combustion efficiency and instantaneous and mineralization current efficiencies were also determined.     

Cathodic reaction kinetics and its implication on flow-assisted corrosion of aluminum alloy in aqueous ethylene glycol solution

The cathodic reaction kinetics and anodic behavior of Al alloy 3003 in aerated ethylene glycol–water solution, under well-controlled hydrodynamic conditions, were investigated by various measurements using a rotating disk electrode (RDE). The transport and electrochemical parameters for cathodic oxygen reduction were fitted and determined. The results demonstrate that the cathodic reaction is a purely diffusion-controlled process within a certain potential region. The experimentally fitted value of diffusion coefficient of oxygen is 3.0 × 10⁻⁸ cm² s⁻¹. The dependence of cathodic current on rotation speed was in quantitative agreement with Levich equation. At potentials more positive than the diffusion controlled region, the cathodic process was controlled by both diffusion and electrochemical kinetics. The electrochemical reaction rate constant, k ₀, was determined to be 1.1 × 10⁻⁹ cm s⁻¹. There is little effect of electrode rotation on anodic behavior of Al alloy during stable pitting. However, fluid hydrodynamics play a significant role in formation of the oxide film and the Al alloy passivity. An enhanced electrode rotation would increase the mass-transfer rate of solution, and thus the oxygen diffusion towards the electrode surface for reduction reaction. The generated hydroxide ions are favorable to the formation of Al oxide film on electrode surface.     

Electrochemical mineralization of sodium dodecylbenzenesulfonate at boron doped diamond anodes

Results are reported of the electrochemical oxidation of sodium dodecylbenzenesulfonate (SDBS), a common surfactant, at boron-doped diamond anodes. The measured critical micelle concentration (CMC) for SDBS in water at 24 °C was almost 150 mg dm⁻³, but this decreased to almost 30 mg dm⁻³ in 0.1 M sodium sulfate. Cyclic voltammetry of a boron doped diamond (BDD) electrode in aqueous SDBS solutions exhibited oxidation current densities at very positive potentials; however, solutions of monomers at concentrations <CMC gave rise to higher current densities than in higher concentration solutions that formed micelles. Galvanostatic electrolyses, with samples analyzed for Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD), were performed in an electrolytic flow cell without separator, operating in batch recycle mode, using solutions containing SDBS at initial concentrations of 25 and 250 ppm. SDBS in basic media (pH = 12) exhibited lower TOC removal rates than in acidic or neutral solutions, due to concurrent oxidation of dissolved carbonates at potentials less positive than required for water oxidation, as evident in cyclic voltammograms. Decreasing the [electrolyte]/[surfactant] ratio from 200 to 10 increased TOC removal rates. For solutions containing monomers, TOC removal rates also increased with flow rate in the second part of the electrolysis, corresponding to reaction of smaller, fragmented organic compounds. When COD removal from a solution containing SDBS micelles was mass transport controlled, current efficiencies were constant at ca. 50%, due to dimerisation of hydroxyl radical to H₂O₂ and its oxidation to dioxygen.     

Electrochemical properties of aluminium anodes for Al/air batteries with aqueous sodium chloride electrolyte

In order to develop the new anode materials for Al/air batteries, electrochemical properties of pure aluminium (99.999 %), technical grade aluminium (99.8 %) and the alloys with indium and tin, i.e. Al—0.1 % In, Al—0.2 % Sn and Al—0.1 % In—0.2 % Sn have been investigated in 2 mol dm⁻³ NaCl solution. The aluminium materials were polarized anodically in the range 20–100 mA cm⁻² for a 30 min period. During the anodic polarization variation in potential was recorded as a function of time and the simultaneous hydrogen evolution was measured. The rate of hydrogen evolution reaction was found to increase with increasing anodic polarization which is characteristic of the negative difference effect. The additional information concerning the corrosion behaviour of the tested materials was provided by light microscope imaging. The results show that the examined technical grade aluminium alloys could serve as suitable anodes for Al/air batteries containing sodium chloride electrolyte; with Al–In exhibiting the most remarkable characteristics. The addition of In as alloying component to aluminium reduces electrode polarization, decreases hydrogen evolution rate and increases the anode efficiency.     

Performance of fluidized bed electrode in a molten carbonate fuel cell anode

A fluidized bed electrode could lower concentration polarization and activation polarization because of its high mass and heat transfer coefficient. The polarization characteristics of the fluidized bed electrode are systematically investigated in a molten carbonate fuel cell anode with an O₂/CO₂/gold reference electrode. The results show that polarization performance of the anode is improved by selecting proper flow rates of H₂, O₂ and CO₂, choosing suitable nickel particle content together with appropriate O₂/CO₂ ratio, and increasing reaction temperature as well as the area of the current collector. Limiting current density of 115.56 mA·cm⁻² is achieved under optimum performance as follows: a cylindrically curved nickel plate current collector, nickel particle content of 7.89%, the reaction temperature of 923 K, H₂ flow rate of 275 mL·min⁻¹, O₂/CO₂ flow rate of 10/20 mL·min⁻¹ and O₂/CO₂ ratio of 1 : 2.     

Investigation of the response of separate electrodes in a polymer electrolyte membrane fuel cell without reference electrode

The paper presents electrochemical measurements carried out in a PEMFC with a view to determining the separate kinetics of the electrode reactions. For this purpose, the separate response of one electrode (anode or cathode) was magnified by dilution of the reacting gas, respectively hydrogen and oxygen, and comparison of the experimental data in the form of steady voltage-current variations and impedance spectra. Experiments were carried out at 60 °C and ambient pressure. Water management was thoroughly controlled so that the gases leaving the cell had the same relative humidity in all experiments of one series. Hydrogen oxidation, although rapid, corresponds to overpotentials up to 50 mV at high dilution rates and current densities. Assuming a Tafel–Volmer mechanism, the exchange current density of the anode reaction at the Pt surface is of the order of 1 mA cm⁻². The two techniques employed led to Tafel slopes of oxygen reduction ranging from 120 to 150 mV/decade, with an exchange current density near 1 μA cm⁻², in good agreement with published data.     

An amorphous Si thin film anode with high capacity and long cycling life for lithium ion batteries

A Si thin film of thickness 275 nm was deposited on rough Cu foil by magnetron sputtering for use as lithium ion battery anode material. X-ray diffraction (XRD) and TEM analysis revealed that the Si thin film was completely of amorphous structure. The electrochemical performance of the Si thin film was investigated by cyclic voltammetry and constant current charge/discharge test. The film exhibited a high capacity of 3,134 mAh g⁻¹ at 0.025 C rate. The capacity retention was 61.3% at 0.5 C rate for 500 cycles. An island structure formed on the Cu foil substrate after cycling adhered to the substrate firmly and provided electrical connection. This is the possible reason for the long cycling life of Si thin film anode. Moreover, the cycling performance was further improved by annealing at 300 °C. The Li⁺ diffusion coefficients (D ₀) of Si thin film, measured by cyclic voltammetry, are 1.47 × 10⁻⁹ cm² s⁻¹ and 2.16 × 10⁻⁹ cm² s⁻¹ for different reduced peaks.     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

有机废水电化学氧化阳极材料的研究进展

阳极材料是电化学氧化法处理有机废水的关键.综述了贵金属电极、碳素电极、钛基金属氧化物电极和合成掺硼金刚石(BDD)薄层电极在内的常用阳极材料的性能,并对有机废水电化学氧化阳极材料的发展趋向进行了展望.     

Electrochemical treatment of water containing chlorides under non-ideal flow conditions with BDD anodes

In this work a undivided parallel plate cell equipped with boron doped diamond (BDD) anode was tested as electrochemical reactor for disinfection of water. Two configurations were adopted: a single pass configuration (SPC) and a recirculated configuration (RC) in which also a reservoir was inserted in the hydraulic circuit. In both the experimental configurations the system worked in continuous mode with a flow rate ranging from 0.05 to 0.42 dm³ min⁻¹; in the RC the recirculating flow rate ranged from 0.45 to 6 dm³ min⁻¹. Thermostated (25 °C) galvanostatic electrolyses were carried out with aqueous solutions containing 100 mg dm⁻³ of chloride ions: values of current density from 2.5 to 5.0 mA cm⁻² were used. Steady state data revealed that active chlorine and chlorate ions were the main oxidation products. Particular attention was paid to the hydrodynamics both for SPC and RC: pulse-response curves were experimentally obtained with an inert tracer, and the behaviour of the system was interpreted by models based on a combination of ideal flow reactors, bypass flow elements, and dead zones. The hydrodynamic models were utilized to predict the outlet concentration of the electrolysis products. A good agreement between model predicted and experimental data was obtained for a wide range of experimental conditions. Preliminary disinfection tests were then performed using Escherichia coli as model microorganism. Results were discussed in terms of both disinfection efficiency and by-products formation.     

Characterization of an electrochemical reactor for the ozone production in electrolyte-free water

The filter-press electrochemical ozonizer is characterized as a function of the applied electric current, temperature, and linear velocity of the electrolyte-free water. Lead dioxide electroformed on surface of a non-platinized fine mesh stainless steel support was used as anode. Electrolysis of the electrolyte-free water was carried out using the membrane electrode assembly (MEA) adequately compressed by means of a specially designed clamping system. Electrochemical characterization studies were carried out galvanostatically as a function of temperature and linear velocity of the circulating water. It was verified that the electrochemical ozone production (EOP) taking place at the reacting zones formed at the solid polymer electrolyte (SPE)/mesh electrode interface is not considerably affected by circulating water when the linear velocity inside the distribution channels is higher than 1.20 cm s⁻¹. A current efficiency for the EOP of 13% and a specific electric energy consumption of 70 Wh g⁻¹ were obtained when an electric current of 130 A was applied at 30 °C. The reactor service life test revealed that the MEA using the lead dioxide fine mesh electrode as anode and a fine mesh stainless steel electrode as cathode, pressed against the SPE, is stable for the ozone production.     

Models of Hypochlorite production in electrochemical reactors with plate and porous anodes

Pseudo two-dimensional finite element models were developed to predict the hypochlorite (chloric(I)) (HOCl + OCl⁻) production by electrolysis of near-neutral aqueous sodium chloride solution, in reactors with (a) an anode and cathode in the form of plates, and (b) a lead dioxide-coated graphite felt anode and titanium plate cathode. The model was used to investigate the feasibility of using a porous anode to achieve high single pass conversions in oxidising chloride ions. For the model reactor with planar anode, the effects of diffusion, migration and convection on the mass transport of the reacting species were considered, whereas with the porous anode, a supporting electrolyte (Na₂SO₄) was notionally present to eliminate the migrational contribution to reactant transport. For an electrolyte flow rate of 10⁻⁶ m³ s⁻¹ (Re = 10 for plate electrodes, Re _porous = 0.76 for porous anode), a cell voltage of 3.0 V and an inlet NaCl of 100 mol m⁻³, the single-pass conversion of Cl⁻ was predicted to increase from 0.45 for the reactor with a planar anode to 0.81 for the reactor with a porous anode. For the same operating conditions, the overall current efficiency was also predicted to increase from 0.71 to 0.77 by replacing the plate with the porous anode.     

Electrochemical polymerisation of phenol in aqueous solution on a Ta/PbO<Subscript>2</Subscript> anode

This paper deals with the treatment of aqueous phenol solutions using an electrochemical technique. Phenol can be partly eliminated from aqueous solution by electrochemically initiated polymerisation. Galvanostatic electrolyses of phenol solutions at concentration up to 0.1 mol dm⁻³ were carried out on a Ta/PbO₂ anode. The polymers formed are insoluble in acidic medium but soluble in alkaline. These polymers were filtered and then dissolved in aqueous solution of sodium hydroxide (1 mol dm⁻³). The polymers formed were quantified by total organic carbon (TOC) measurement. It was found that the conversion of phenol into polymers increases as a function of initial concentration, anodic current density, temperature, and solution pH. The percentage of phenol polymerised can reach 15%.     

Electrochemical characteristics of boron doped polycrystalline diamond electrode sintered by high pressure and high temperature

The bulk B-doped polycrystalline diamond (PCD) electrode in this study was prepared by high-pressure, high-temperature (HPHT) technology. The PCD was sintered under HPHT conditions, using B-doped diamond powders and a metal catalyst as raw materials, then the metal solvent phase was dissolved by aqua regia. The morphology and composition of the PCD were investigated with a scanning electron microscope (SEM), X-ray diffraction (XRD), and energy dispersion spectrum (EDS). The results show that the sintered body possesses a polycrystalline structure with direct diamond–diamond bond and irregularly shaped pores of 1–10 μm distributed on the grain boundaries after the metal solvent phase was removed. The cyclic voltammogram and electrochemical impedance spectroscopy of this B-doped electrode have been investigated. The B-doped PCD electrode exhibits stable electrochemistry in a KCl support solution over a wide potential range. The quasi-reversible reaction occurs on the electrode for the [Fe(CN)₆]^3−/4− couples. The electrode process combines the diffusion-controlled mass transport plus the kinetic process. The electrochemical impedance spectroscopy (EIS) analysis shows the porous structure characteristic of the PCD electrode.