Modified titanium electrodes: Application to Ti/TiO2/PbO2 dimensionally stable anodes

Titanium is a valve metal able to withstand corrosion, due to the presence of a passivating layer of titanium oxide on its surface. But, due to that more or less insulating layer, titanium cannot be used directly as an anodic material. However, modification of the surface of a Ti/TiO₂ substrate may lead to the formation of new structures: Ti/TiO₂/M or Ti/TiO₂/OX, in which M is a metal such as platinum and OX a conducting oxide exhibiting electrocatalytic properties. These structures have interesting electrochemical properties and may be used as efficient electrode materials.In this paper, after a review of the electrochemical behaviour of these structures, we give new results concerning the selective electrodeposition of lead dioxide on Ti/TiO₂ substrates and we propose an interpretation of the results taking into account the dielectric properties of the underlying TiO₂. It is shown that there is a dramatic decrease of the resistance of the electrode when a PbO₂ layer is electrodeposited onto a Ti/TiO₂ structure. That effect allows the preparation of electrodes (low-cost DSAs) that may be used as anodes in spite of the presence of the underlying TiO₂ layer, that layer being useful to avoid corrosion of the titanium substrate. At last, the effect of stabilization of the underlying TiO₂ layer is discussed.     

A study of the deactivation and service life of Ir oxide anodes supported on Al substrates

The deactivation of Ir oxides supported on Al substrates has been studied in 0.5 M H₂SO₄. Their electrochemical behaviour and service life was also compared to IrO₂ electrodes, similarly prepared, supported on Ti. The Ir oxides were prepared by thermal decomposition of an Ir salt precursor solution. The service life and other oxide properties were found to be influenced by different factors used for preparation of the Ir oxide electrodes, for example, the temperature used for the decomposition process and the solution used to etch the Al substrate. In contrast to the IrO₂ anodes supported on Ti, the service lives of the IrO₂ anodes supported on Al were found to be very short. The deactivation of the latter anodes appears to be related to poor adhesion between the Ir oxide and the Al substrate. However, it was found that the service life of IrO₂ anodes supported on Al is increased when a layer consisting of iridium is electrochemically deposited onto the Al substrate prior to the thermal formation of the IrO₂.     

Phase and Texture Evolution in Chemically Derived PZT Thin Films on Pt Substrates

The crystallization of lead zirconate titanate (PZT) thin films was evaluated on two different platinum‐coated Si substrates. One substrate consisted of a Pt coating on a Ti adhesion layer, whereas the other consisted of a Pt coating on a TiO₂ adhesion layer. The Pt deposited on TiO₂ exhibited a higher degree of preferred orientation than the Pt deposited on Ti (as measured by the Full Width at Half Maximum of the 111 peak about the sample normal). PZT thin films with a nominal Zr/Ti ratio of 52/48 were deposited on the substrates using the inverted mixing order (IMO) route. Phase and texture evolution of the thin films were monitored during crystallization using in situ X‐ray diffraction at a synchrotron source. The intensity of the Pt₃Pb phase indicated that deposition on a highly oriented Pt/TiO₂ substrate resulted in less diffusion of Pb into the substrate relative to films deposited on Pt/Ti. There was also no evidence of the pyrochlore phase influencing texture evolution. The results suggest that PZT nucleates directly on Pt, which explains the observation of a more highly oriented 111 texture of PZT on the Pt/TiO₂ substrate than on the Pt/Ti substrate.     

Electro-oxidation of coal on NiO and/or Co3O4 modified TiO2/Pt electrodes

A TiO₂/Pt based electrode exhibited better activity for the oxidation of coal in a basic system compared to Ti/Pt, TiO₂–Cu/Pt and pure metal electrodes. The surface morphologies and composition of the electrodes were studied by SEM and XRD, respectively. Linear sweep voltammetry was employed to investigate the catalytic effects of electrodes, and the product of coal oxidization was determined by a gas collection test. The TiO₂/Pt electrodes that were modified with NiO and/or Co₃O₄ exhibited higher average currents and a lower decrease in mass during electrolysis compared to the other electrodes; this finding indicated that NiO and Co₃O₄ play important roles as catalysts.     

Cr(III) oxidation with lead dioxide-based anodes

A procedure for preparing PbO₂-based electrodes with a titanium substrate is proposed. A platinum underlayer is first deposited on Ti by metal organic chemical vapor deposition (MOCVD), followed by the electrodeposition of the PbO₂ layer. The prepared Ti/Pt/PbO₂ anodes were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD) before being used for oxidation of Cr(III) in sulphuric acid. The current efficiency was determined for that electrodes and the results were compared with those obtained with Pb/PbO₂ and Ebonex^®/PbO₂ electrodes with different pH conditions. The Ti/Pt/PbO₂ were found to have a very good electrochemical behaviour (current efficiency: φ=0.93 for pH 2), and may be used as dimensionally stable anodes for the oxidation of Cr(III).     

Deposition of tin oxide,iridium and iridium oxide films by metal-organic chemical vapor deposition for electrochemical wastewater treatment

In this research, the specific electrodes were prepared by metal-organic chemical vapor deposition (MOCVD) in a hot-wall CVD reactor with the presence of O₂ under reduced pressure. The Ir protective layer was deposited by using (Methylcyclopentadienyl) (1,5-cyclooctadiene) iridium (I), (MeCp)Ir(COD), as precursor. Tetraethyltin (TET) was used as precursor for the deposition of SnO₂ active layer. The optimum condition for Ir film deposition was at 300 °C, 125 of O₂/(MeCp)Ir(COD) molar ratio and 12 Torr of total pressure. While that of SnO₂ active layer was at 380 °C, 1200 of O₂/TET molar ratio and 15 Torr of total pressure. The prepared SnO₂/Ir/Ti electrodes were tested for anodic oxidation of organic pollutant in a simple three-electrode electrochemical reactor using oxalic acid as model solution. The electrochemical experiments indicate that more than 80% of organic pollutant was removed after 2.1 Ah/L of charge has been applied. The kinetic investigation gives a two-step process for organic pollutant degradation, the kinetic was zero-order and first-order with respect to TOC of model solution for high and low TOC concentrations, respectively.     

An innovative approach to electro-oxidation of dopamine on titanium dioxide nanotubes electrode modified by gold particles

Au/TiO₂/Ti electrodes were prepared by galvanic deposition of gold particles from an acidic bath containing KAu(CN)₂ in the presence of a citrate buffer onto TiO₂ nanotubes layer on titanium substrates. Titanium oxide nanotubes were fabricated by anodizing titanium foil in a DMSO fluoride-containing electrolyte. The morphology and surface characteristics of Au/TiO₂/Ti electrodes were investigated using scanning electron microscopy and energy-dispersive X-ray, respectively. The results indicated that gold particles were homogeneously deposited on the surface of TiO₂ nanotubes. The nanotubular TiO₂ layers consist of individual tubes of about 40–80 nm diameters. The electro-catalytic behavior of Au/TiO₂/Ti electrodes for the dopamine electro-oxidation was studied by cyclic voltammetry and differential pulse voltammetry. The results showed that Au/TiO₂/Ti electrodes exhibit a considerably higher electro-catalytic activity toward the oxidation of dopamine. The catalytic oxidation peak current showed a linear dependence on dopamine concentration and a linear calibration curve was obtained in the concentration range of 0.5–2.5 mM of dopamine.     

Electrochemical treatment of aqueous solutions containing urea

Investigations on the anodic decomposition of urea using Ti/Pt and Ti/(RuO₂–TiO₂)_40:60 electrodes were carried out. The kinetics of the process were examined in a periodic electrolyser. The effect of anodic current density, initial urea concentration, and sodium chloride concentration on the effectiveness of the basic process (average rate of urea decomposition, current efficiency, and unit power consumption) is discussed. When a Ti/Pt electrode is applied for urea removal from aqueous solution urea is not decomposed directly at the surface of the electrode, but rather in the bulk of the solution by hypochlorite formed during the process. When the Ti/(RuO₂–TiO₂)_40:60 electrode is used for the removal of urea from aqueous solutions, the reaction of urea with chlorine adsorbed at the electrode predominates. In both cases non-toxic products of urea decomposition (N₂, CO₂,) are formed. Comparison of the effectiveness of anodic decomposition of urea for the Ti/Pt and Ti/(RuO₂–TiO₂)_40:60 electrodes in the periodic electrolyser at optimum process parameters has revealed that the former electrode is more favorable.     

Electroxidation of oxalic acid at different electrode materials

Oxalic acid is one of the proposed metabolites of the anodic oxidation of more complex organic molecules. In spite of its simple structure, its mineralization strongly depends on the nature of the electrode material at which the process is carried out. Sargisyan and Vasil’ev (Elektrokhimiya 18:845, 1982) pointed out such dependence, investigating the kinetic behavior of OA at different metal (Rh, Pd, Os, Ir, Pt and Au), at dimensionally stable anodes (RuO₂–TiO₂) and at glassy carbon (GC) electrodes. Their conclusions highlighted the important role played by the organic anion adsorption step, claiming that OA is oxidized with increasing difficulty at electrode materials having higher oxygen affinity. More recently, these assumptions have been supported by data on OA oxidation at high anodic potentials (Martínez-Huitle et al., Electrochim Acta 49:4027, 2004). To further enrich the picture, in the present paper, kinetic investigations were carried out at different mixed-oxides, Pt, GC and highly conductive, boron-doped diamond (BDD) electrodes, with either oxygen or fluorine at their surface.     

Electrochemical behaviour of titanium(II) and titanium(III) compounds in molten lithium chloride/ potassium chloride eutectic melts

The nature of the open circuit potentials of Ti and TiC electrodes in titanium(II) and titanium(III) chloride solutions, the apparent valency of the titanium ions in the melt immediately after the anodic dissolution of TiC and Ti, as well as the anodic dissolution of Ti, have been investigated in order to explain the oxidation-reduction process of titanium in lithium chloride-potassium chloride eutectic melts. It is shown that the standard electrode potential for TiC/Ti(III) exceeds that for the oxidation of Ti(II) to Ti(III). The anodic dissolution of TiC anodes give stable Ti(III) species at the standard electrode potentials the contrary to the behaviour of Ti metal anodes where the stable species are Ti(II) ions. Titanium electrodes in TiCl₃ solutions of molten lithium chloride-potassium chloride melts behave according to the Ti(III)/Ti(II) redox electrode potential of the reaction: Ti+TiCl₃3TiCl₂. An anodic dissolution mechanism compatible with all the experimental facts is proposed.     

On the composition and structure of thin layers of titanium oxide on platinum surfaces

This work reviews the available data about the structure and composition of thin layers of titanium oxide on the surface of platinum. These systems can be prepared by vapor deposition and subsequent oxidation of Ti on a massive Pt substrate or by oxidation at low pressure of the Pt₃Ti alloy. For both types of substrate, the XPS data show that two distinct Ti states in the oxide layer can be detected. The structure and the composition of the oxide layer varies depending on the substrate composition and on the conditions of preparation. On pure Pt, the preferential formation of a defective TiO_2–x oxide was observed. On Pt₃Ti, the oxide film a layer was formed of TiO of thickness of the order of a single atomic layer and of crystallites of nearly stoichiometry TiO₂.     

The oxygen evolution reaction on platinum,iridium, ruthenium and their alloys at 80°C in acid solutions

Kinetic parametes were determined for the oxygen evolution reaction on 50–50 atom percent alloys of RuIr, RuPt, and IrPt and compared with results obtained using ruthenium, iridium, platinum, and RuO₂/TiO₂ electrodes. The potentiostatic studies were made on oxide covered electrodes at 80°C in both 1.0 M H₂SO₄ and 1.0 M CF₃SO₃H. Cyclic voltammetric studies showed that while these noble metals and alloys are about equally effective as electrocatalysts for the hydrogen evolution reaction, striking differences in activity are found for the oxygen evolution reaction. The order of electrocatalytic activity towards oxygen evolution in H₂SO₄ is Ru > RuIr alloy ～ RuO₂/TiO₂ ～ Ir > IrPt alloy > RuPt alloy > Pt. The type of acid used had very little effect on the kinetic parameters. The lower electrocatalytic activities when platinum is present is probably due to the formation of a platinum oxide film. The dual barrier model is used to interpret the results for the electrodes containing platinum. The best electrocatalysts for oxygen evolution in acid solutions consist of noble metals which form oxide films (RuO₂, IrO₂) possessing metallic characteristics.     

The anodic characteristics of modified Mn oxide electrode: Ti/RuOx/MnOx

The Ti-supported Mn oxide electrode was modified by introducing a Ru oxide film as an intermediate layer into the Ti/Mn oxide interface, and its anodic characteristics were examined in aqueous solutions of 0.5 M H₂SO₄, 1 M KOH and 5 M NaCl. The intermediate thin film of the Ru oxide served effectively as a good conductor to improve the electric characteristics of the Ti-supported Mn oxide electrode and hence the modified electrode exhibited the excellent anodic characteristics similar to those of the Pt-based Mn oxide. From the kinetic considerations, it was proved that the anodic evolution of oxygen takes place on the surface of Mn oxide. The Mn oxide was found to be virtually active electrocatalyst for electrolytic chlorine evolution as well as electrolytic oxygen evolution. As a result of the evaluation of the catalytic activity, it was considered that the Mn oxide is one of the most active material of all, except for some DSA-type electrodes such as Ru and Ir oxides, for the anodic evolution of oxygen. In conclusion, the presented results suggest that the modified Mn oxide electrode has a promising character for the practical use in water electrolysis.     

Matériaux anodiques pour électrolyseurs

This paper is a review of the main anodic materials (including coatings) used in industrial electrochemical cells. The mechanism of the electrochemical reactions is given in detail; many examples of applications as well as the probable new developments in electrode materials are discussed. An important part of the paper is devoted to carbon and precious metal oxides coatings on a valve metal substrate such as titanium, leading to dimensionally stable anodes (DSA). The mechanism of the deactivation process of DSA is described: the passivation is due to the formation of a passivating TiO₂ layer between the titanium substrate and the electrocatalytic coating.     

Selective electrodeposition of PbO2 on anodised-polycrystalline titanium

Electrochemical experiments on titanium electrodes were coupled with electron backscattered diffraction (EBSD) experiments. The substrates were thermally treated and electropolished in order to have flat and reproducible polycrystalline surfaces, leading to EBSD orientation mapping. Afterwards, the samples were anodised by a galvanostatic procedure. It was shown that electrodeposition of PbO₂ from a 0.5 M Pb(NO₃)₂+2.5 M HNO₃ solution occurs selectively on the near {0 0 0 1} grains, whereas lead electrodeposition occurs on all the grains, whatever their orientation. These results are discussed, taking into account the fact that on {0 0 0 1} grains, the oxide layers are thinner than on other grains. It was concluded that electrodeposition is observed locally on Ti/TiO₂ electrodes for (i) cathodic electrodeposition of metals at low overvoltage; (ii) anodic electrodeposition of PbO₂, in potentiostatic or galvanostatic conditions.     

Electrical properties of sputtered PZT films on stabilized platinum electrode

PZT (54/46) thin films were deposited by r.f. magnetron sputtering followed by a post-annealing treatment on silicon substrates. The crucial role of a Ti adhesion layer on the Ti/Pt bottom electrode is presented. The deposition conditions and the thickness of Ti have dominant effects on the interactions between Ti and Pt during the annealing treatment. The Pt layer, whatever its thickness, did not act as a barrier against Ti-out diffusion. The stability of the bottom electrode was achieved by using a TiO_x layer instead of a pure metallic Ti adhesion layer. The electrical properties of PZT films in terms of dielectric and ferroelectric performance were evaluated, particularly as a function of the PZT film thickness.     

Catalytic and photocatalytic effects on photoplatinized macroscopic TiO2 photoanodes in dilute ethanol solutions

TiO₂, platinized TiO₂, and platinized Pt anodes have been studied in both acidic and basic electrolytes in the presence of ethanol. In the case of macroscopic platinized TiO₂ anodes, the oxidation of ethanol to acetaldehyde and the further oxidation of acetic acid is predominantly a catalytic rather than a photocatalytic effect, and can be accomplished in the dark with a bias voltage of approximately 0.6 V. This same result has been shown to occur with platinized Pt electrodes in the absence of TiO₂. Cyclic voltammetry studies suggest that oxidation of acetic acid, previously reported in particulate platinized TiO₂ systems, requires the production of the highly reactive OH radical. Thus both catalytic and photocatalytic processes are occuring simultaneously at illuminated platinized TiO₂ anodes.     

Electrophoretic deposition of nanocrystalline hydroxyapatite on Ti6Al4V/TiO2 substrate

Hydroxyapatite is a bioactive material that is the main inorganic constituent of human hard tissue (Ca/P ratio of 1.67) whose coatings provide requisite surface bioactivity to the bone implants. In the current work, the characteristics of nanocrystalline hydroxyapatite (HA) coatings, electrophoretically deposited on Ti6Al4V substrate, have been investigated. To enhance the coating’s compatibility, a 0.75 μm thick TiO₂ layer was thermally grown as a diffusion barrier prior to electrophoretic deposition of HA. Subsequently, HA was electrophoretically deposited (EPD) at different deposition voltages (100–250 V) while keeping the deposition time as 10 s. Both anodic oxidation during EPD for 10 s and thermal oxidation during sintering at 1000°C for 2 h resulted in the growth of a TiO₂ layer thickness of more than 25 μm. Enhancement of voltage also has shown significant influence on the mechanism of the evolution of biphasic microstructures, attributed to the simultaneous growth of TiO₂ and HA phases. Optimized distribution of HA and TiO₂ phases was evidenced at 200 V, with explicit HA retention as observed via transmission electron microscopy. An empirical relationship is developed to relate the voltage with the suppression of cracking in the deposited coatings.     

Electrochemical deposition of aluminium on tungsten in cryolite based melts

Aluminium deposition and redissolution on tungsten electrodes in cryolite melts of different NaF/AlF₃ ratios have been investigated by potential sweep and galvanostatic techniques. The amount of charge necessary for anodic reoxidation of deposited aluminium was determined as well as the rate of spontaneous corrosion. The qualitative results obtained can be interpreted by assuming a mass transport controlled loss reaction involving metal dissolution in the melt.     

Electrochemical oxidation of ammonia (NH4/NH3) on thermally and electrochemically prepared IrO2 electrodes

The electrochemical oxidation of ammonia (NH₄⁺/NH₃) in sodium perchlorate was investigated on IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor and the anodic oxidation of metallic iridium. The electrochemical behaviour of Ir(IV)/Ir(III) surface redox couple differs between the electrodes indicating that on the anodic iridium oxide film (AIROF) both, the surface and the interior of the electrode are electrochemically active whereas on the thermally decomposed iridium oxide films (TDIROF), mainly the electrode surface participates in the electrochemical processes.On both electrodes, ammonia is oxidized in the potential region of Ir(V)/Ir(IV) surface redox couple activity, thus, may involve Ir(V). During ammonia oxidation, TDIROF is deactivated, probably by adsorbed products of ammonia oxidation. To regenerate TDIROF, it is necessary to polarize the electrode in the hydrogen evolution region. On the contrary, AIROF seems not to be blocked during ammonia oxidation indicating its fast regeneration during the potential scan. The difference between both electrodes results from the difference in the activity of the iridium oxide surface redox couples.