Investigation of formic acid oxidation on Ti/IrO2 electrodes

A model has been proposed according to which the voltammetric charge involved in the Ti/IrO₂ electrodes is due to two contributions: a faradaic contribution due to surface redox activities at the IrO₂ coating and a non-faradaic contribution due to the charging of electrical double layer (). The later has been proposed as a tool for the estimation of the relative surface area of the Ti/IrO₂ electrodes.Differential electrochemical mass spectrometry (DEMS) measurements using H₂¹⁸O has demonstrated that we are dealing with an active electrode in which the surface redox couple IrO₃/IrO₂ acts as mediator in the oxidation of formic acid (FA).From the voltammetric measurements using different IrO₂ loading and FA concentrations, the kinetic parameters of FA oxidation via the surface redox couple IrO₃/IrO₂ have been determined.Finally a model has been proposed considering that FA oxidation at Ti/IrO₂ anodes is controlled by mass transfer. The good agreement between the experimental results and the model indicates that the surface reaction between FA and the electrogenerated IrO₃ is a fast reaction.     

The importance of electrode material in environmental electrochemistry: Formation and reactivity of free hydroxyl radicals on boron-doped diamond electrodes

A model describing the hydroxyl radical (HO) concentration profile at the boron-doped diamond (BDD) electrode, in the presence and absence of organic compounds, is presented. It is shown that this profile depends strongly on the reaction rate constant between the HO and the organic compound. Furthermore, it is shown that the presence of organics affects the current-potential (I-V) curves. In fact, the higher the reaction rate between organics and HO, the higher is the shift of the I-V curves toward lower potential with respect to oxygen evolution. Supposing that water discharge to free hydroxyl radicals on BDD is governed by Nernst equation, this shift of the I-V curves toward lower potentials has been calculated and compared with the experimental data obtained on BDD using two model compounds: methanol and formic acid.     

Effectiveness factor of isopropanol oxidation on IrO2 based electrodes of different loading

The influence of IrO₂ loading on the effectiveness factor E_f of the electrochemical oxidation of isopropanol was investigated. A model has been proposed based on three main reactions: electrochemical IrO₂ oxidation to IrO₃, chemical oxidation of the organic compound via IrO₃ and O₂ evolution via decomposition of IrO₃. It has been found that the relative effectiveness factor E_f for the electrochemical oxidation of IrO₂ to IrO₃ is loading independent contrary to the chemical reaction which decreases with increasing IrO₂ loading.     

The effects of the temperature on the some parameters obtained from current-voltage and capacitance-voltage characteristics of polypyrrole/n-Si structure

The polypyrrole/n-Si structure has been directly formed onto the n-Si substrate by the electrochemical polimerization of the organic polypyrrole at 45 °C electrolyte temperature. The current-voltage (I-V) and capacitance-voltage (C-V) characteristics of the structure have been determined at various temperatures in the range of 77-300 K and different frequencies. Some diode parameters have been calculated from these curves. It has been seen that the measured capacitance decreases with increasing frequency due to a continuous distribution of the interface states in the frequency range of 10 kHz-1 MHz. The barrier heights values obtained from the I-V and C-V characteristics have been compared. It has been seen that the barrier height value obtained from the C-V measurements are higher than that obtained from the I-V measurements at various temperatures. This behaviour has been attributed to the interfacial layer, the interface states and barrier inhomogeneity of the structure. Also this discrepancy can be due to the different nature of the C-V and I-V measurement techniques. A correlation seems to exist between the variation of the band gap and Fermi level energy of Si with temperature.     

Application of chronopotentiometry and derivative chronopotentiometry with an alternating current to the study of a slow charge transfer in a surface confined redox system

General analytical expressions for the potential-time (E-t) and derivative-potential ((dt/dE)-E) curves of a electroactive monolayer exhibiting a quasi-reversible behaviour, corresponding to the application of an alternating current time function of the form I(t) = I₀ cos(ωt), are presented. The use of this programmed current gives rise to singular and characteristic electrochemical responses. The alternating current also allows to obtain cathodic or both anodic and cathodic responses depending on whether the depletion of the adsorbed species was complete or not, and without using more than one applied current. Moreover, in this last case, it is possible to distinguish a reversible or an irreversible process by means of a simple visualisation of the E-t or (dt/dE)-E curves. Easy methods for estimating thermodynamic and kinetic parameters of the electroactive film are proposed and experimentally tested and compared with those previously obtained by using Cyclic Voltammetry.     

Electrocatalytic activity of IrO2-RuO2 supported on Sb-doped SnO2 nanoparticles

Electrocatalytic IrO₂-RuO₂ supported on Sb-doped SnO₂ (ATO) nanoparticles is very active towards the oxygen evolution reaction. The IrO₂-RuO₂ material is XRD amorphous and exists as clusters on the surface of the ATO. Systematic changes to the surface chemical composition of the ATO as a function of the IrO₂:RuO₂ ratio suggests an interaction between the IrO₂-RuO₂ and ATO. Cyclic voltammetry indicates that the electrochemically active surface area of IrO₂-RuO₂ clusters is maximised when the composition is 75 mol% IrO₂-25 mol% RuO₂. Decreasing the loading of IrO₂-RuO₂ on ATO reduces the electrochemically active surface area, although there is evidence to support a decrease in the clusters size with decreased loading. Tafel slope analysis shows that if the clusters are too small, the kinetics of the oxygen evolution reaction are reduced. Overall, clusters of IrO₂-RuO₂ on ATO have similar or better performance for the oxygen evolution reaction than many previously reported materials, despite the low quantity of noble metals used in the electrocatalysts. This suggests that these oxides may be of economic advantage if used as PEM water electrolysis anodes.     

Study of carbon-supported IrO2 and RuO2 for use in the hydrogen evolution reaction in a solid polymer electrolyte electrolyzer

Carbon-supported IrO₂ and RuO₂ were prepared using an incipient wetness method and were then calcinated at various temperatures. IrO₂/C and RuO₂/C are less expensive than the conventional Pt/C material and more stable than metal Ni in an acidic electrolyte. Moreover, IrO₂/C and RuO₂/C are not influenced by under potential deposition (UPD) and show lower sensitivity to poisoning by Ni or Fe impurities. The physical properties of IrO₂/C and RuO₂/C were investigated via XRD and TEM. Cyclic voltammograms (CV) and Tafel plots were used to provide information regarding surface redox reaction and electrocatalytic activity. The activity and durability of IrO₂/C and RuO₂/C were studied after prolonged potential cycling between −0.3 and 0.3 V_SCE. After comparison of Tafel plots of Pt/C and IrO₂/C after activation, it was observed that they have similar electrocatalytic activities in a hydrogen evolution reaction (HER). A single cell test with solid polymer electrolyte (SPE) proved that the performance of IrO₂/C (0.5 mg cm⁻²) was similar to that of Pt/C (0.5 mg cm⁻²).     

Long-term cyclability and high-rate capability of Li3V2(PO4)3/C cathode material using PVA as carbon source

The Li₃V₂(PO₄)₃/C composite cathode material is synthesized via a simple carbothermal reduction reaction route using polyvinyl alcohol (PVA) as both reduction agent and carbon source. The XRD pattern shows that the as-prepared Li₃V₂(PO₄)₃/C composite has a monoclinic structure with space group P2₁/n. The result of XPS shows the oxidation state of V in the Li₃V₂(PO₄)₃/C composite is +3. The Raman spectrum reveals that the coating carbon has a good structure with a low I_D/I_G ratio. The high-quality carbon can not only enhance the electronic conductivity of the Li₃V₂(PO₄)₃/C composite but also prevent the growth of the particle size. The electrochemical performance, which is especially notable for its high-rate performance, is excellent. It delivers an initial discharge capacity of 105.3 mAh/g at 5 C, which is retained as high as 90% after 2000 cycles. No capacity loss can be observed up to 300 cycles under 20 C rate condition. Our experimental results suggest that this compound can be a candidate as cathode materials for the power batteries of hybrid electric vehicles (HEVs) and electric vehicles (EVs) in the future.     

Simulations and study of electrochemical hydrogen energy conversion in EasyTest Cell

An EasyTest Cell concept is applied to study the performance characteristics of the electrochemical processor for polymer electrolyte membrane electrochemical hydrogen energy converters (PEM EHEC), broadly known as a membrane electrode assembly (MEA). A series of MEAs consisting of Nafion 117 polymer electrolyte and magnetron sputtered Pt, IrO_x, and composite IrO_x/Pt/IrO_x catalysts with varying catalytic loadings were investigated. The partial electrode reactions proceeding in the real PEM EHEC, namely hydrogen oxidation (HOR), hydrogen evolution (HER), oxygen reduction (ORR), and oxygen evolution (OER), are simulated and studied in a recently developed test cell with a unitized gas compartment. The EasyTest Cell design gives possibilities for strict control of the experimental conditions by avoiding the usage of any auxilliary gas conditioning equipment. By varying the thickness of the sputtered Pt film, the catalyst loading is remarkably reduced (from 0.5 to 0.06 mg cm⁻² or about 8 times) for both HOR and HER without any sacrifice of the electrode performance. The electrode with 0.2 mg cm⁻² sputtered IrO_x shows the best OER performance. The composite IrO_x/Pt/IrO_x electrode demonstrated a bi-functional catalytic activity toward both OER and ORR, as well as improved gas diffusion properties toward ORR compared to the single Pt layer with the same catalytic loading.A phenomenological criterion for evaluating the gas diffusion properties of the electrodes is proposed. The applied testing approach is validated via comparison of the results obtained in the EasyTestCell and the common laboratory PEM electrolytic cell.     

Improved performance of dense TiO2/CdSe coupled thin films by low temperature process

Dense TiO₂ and TiO₂/CdSe coupled nanocrystalline thin films were synthesized onto ITO coated glass substrate by chemical route at relatively low temperature (≤100 °C). TiO₂ films were nanocrystalline and crystallinity disappears after CdSe deposition as evidenced by X-ray powder diffraction. Surface morphology and physical appearance of films were studied from SEM and actual photo-images, reveals dense nature of TiO₂ (10-12 nm spherical grains, faint violet) and CdSe (80-90 nm spherical grains, deep brown), respectively. Presence of two absorption edges in UV spectra implies existence of separate phases rather than composite formation. TiO₂ film was found to have higher water contact angle (71°) than TiO₂/CdSe (61°) and CdSe (56°). I-V and stability tests of photo-electrochemical cells were performed with TiO₂ and TiO₂/CdSe film electrodes (under light of illumination intensity 80 mW/cm²) in lithium iodide as an electrolyte using two-electrode system.     

A study on performance improvement of Ir oxide-coated titanium electrode for organic destruction

The performance improvement of IrO₂ electrode for the oxidative destruction of organics through evaluations of the electrode in terms of material, electrochemical, and destruction organic properties has been carried out by using TGA, XPS, AES, and TOC measurement of 4CP organic destruction at the electrode. A sintering temperature of around 650 °C rather than 400-550 °C suggested in the literature for the Ir oxide electrode enhanced the organic destruction yield because the electrode surface was sufficiently converted to IrO₂ from the IrCl₃ of the precursor solution. An additional oxide layer between the IrO₂ layer and the Ti substrate, to prevent a solid diffusion of TiO₂ due to oxidation of the Ti substrate during high-temperature sintering, further improved the organic destruction so that the 4CP destruction yield raised to about four times higher than that by the conventional Ir oxide electrode. The destruction yield of 4CP solution with chloride ion at the improved electrode increased as much as that by an RuO₂ electrode sintered at 430 °C in the same solution. The improved Ir oxide electrode had a long lifetime and good production of active chloride compounds.     

MOCVD-derived GdYBCO tapes with smooth surface and low Rs based on a new self-heating technology

The metal organic chemical vapor deposition (MOCVD) method was used to prepare GdYBCO films on LaMnO₃/ homo epitaxial-MgO/ ion-beam-assisted-deposition-MgO/ solution-deposition-planarization-Y₂O₃ buffered Hastelloy tapes. By adopting a simple self-heating technique, the substrates were heated by the joule effect after applying a heating current (I_h) through Hastelloy metal tapes. The effects of substrate temperature and (Gd, Y)/Ba ratio (r_c) in the precursor on the biaxial texture, surface morphology and superconducting performance of GdYBCO films were systematically investigated by varying the values of I_h and r_c. Needle-like outgrowths formed on the substrate surface were characterized using a scanning electron microscope, energy dispersive spectrometer and X-ray diffraction system. The results show that a high I_h or r_c leads to the formation of needle-like outgrowths. Therefore, I_h and r_c are crucial process parameters that control the growth of needle-like outgrowths on the surface of GdYBCO films. Three hundred nanometer thick GdYBCO films were prepared at different I_h and r_c by the MOCVD process. At an I_h of 27.0?A and an r_c of 0.6, the surface of the GdYBCO film was very smooth and dense, which can provide a good template for multiple depositions of GdYBCO films. The critical current density of the deposited 300?nm-thick GdYBCO film was 4.4 MA/cm² (77?K, 0?T), which is attributed to good biaxial texture and appropriate film composition. Furthermore, the microwave surface resistance (77?K, 10?GHz) of the GdYBCO film was merely 0.581?mΩ.     

The effects of the time-dependent on the characteristic parameters of polypyrrole/p-type Si/Al diode

A detailed study of the effects of the time-dependent or aging on the characteristic parameters of polypyrrole/p-type Si/Al structure has been presented. The polypyrrole film has been formed on a p-type Si substrate by means of an anodization process. The polypyrrole/p-Si contact has demonstrated clearly rectifying behavior by the current-voltage curves studied at room temperature. The current-voltage (I-V) curves of the diode have been measured immediately, 7, 15, 30, 60 and 90 days after fabrication of the polypyrrole/p-Si contact. It has been seen that the characteristics parameters such as barrier height, ideality factor and series resistance of polypyrrole/p-type Si/Al structure have changed with increasing ageing time. Furthermore, the density distribution of interface states of the device was obtained from the forward bias I-V characteristics. The fact that the diode shows non-ideal I-V behavior with increasing ageing time may be ascribed to a slow replacement of the initial doping agent by oxygen and this process certainly plays a role in the aging of the diode.     

Influence of the V2O5 Loading on the Structure and Activity of V2O5/TiO2 SCR Catalysts for Vehicle Application

In this paper the effect of the vanadium oxide loading on the surface vanadia structure and the activity as well as selectivity in the catalytic reduction of NO with NH₃ was studied for a V₂O₅/TiO₂ model system. A series of TiO₂ (WO _x stabilized anatase) supported vanadia catalysts with varying loadings were characterized by laser Raman spectroscopy, ⁵¹V MAS-NMR, V K XANES. To determine the acidic properties, DRIFTS measurements were done with pyridine adsorbed on the samples. The measurements indicate that with increasing active phase loading square pyramidal coordinated surface vanadia species are replaced by an amorphous highly dispersed vanadium oxide phase with a coordination like V₂O₅. In addition, the ratio of Brønsted to Lewis acid sites is shifted from a comparatively low to an equal level at high loadings. This structural change is accompanied by a clearly improved catalytic activity and selectivity.     

Effect of oxygen sintering atmosphere on the electrical behavior of CCTO ceramics

The CaCu₃Ti₄O₁₂ ceramics were sintered in air and pure O₂ atmosphere, respectively, and the effect of pure O₂ atmosphere on the electrical behavior of the CaCu₃Ti₄O₁₂ ceramics was investigated. It was found that the dielectric properties of the CaCu₃Ti₄O₁₂ ceramics displayed a Debye-like relaxation between 20 Hz and 1 MHz, but the permittivity of the sample sintered in pure O₂ atmosphere was decreased drastically. Moreover, the I-V behavior of the ceramic sintered in pure O₂ atmosphere presented a linear feature. With XPS analysis, it was illustrated that the valence of Cu and Ti elements in the CaCu₃Ti₄O₁₂ ceramics had obviously been influenced by the O₂ concentration. Based on the experimental comparison of CaCu₃Ti₄O₁₂ ceramics sintered in air and pure O₂ atmosphere, it was suggested that the valence of metallic elements and defects played key role for the origin of the giant permittivity and I-V nonlinear feature in the CaCu₃Ti₄O₁₂ ceramics.     

A promising sol-gel route based on citric acid to synthesize Li3V2(PO4)3/carbon composite material for lithium ion batteries

Li₃V₂(PO₄)₃/carbon composite material was synthesized by a promising sol-gel route based on citric acid using V₂O₅ powder as a vanadium source. Citric acid acts not only as a chelating reagent but also as a carbon source, which enhance the conductivity of the composite material and hinder the growth of Li₃V₂(PO₄)₃ particles. The structure and morphology of the sample were characterized by TG, XRD and TEM measurements. XRD results reveal that Li₃V₂(PO₄)₃/carbon was successfully synthesized and has a monoclinic structure with space group P2₁/n. TEM images show Li₃V₂(PO₄)₃ particles are about 45 nm in diameter embeded in carbon networks. Galvanostatic charge/discharge and cyclic voltammetry measurements were used to study its electrochemical behaviors which indicate the reversibility of the lithium extraction/insertion processes. Li₃V₂(PO₄)₃/carbon performed in a voltage window (3.0-4.8 V) exhibits higher discharge capacity, better cycling stability and its discharge capacity maintains about 167.6 mAh/g at a current density of 28 mA/g after 50 cycles.     

Adsorption and oxidation of NH3 over V2O5/AC surface

V₂O₅/AC has been reported to be active for selective catalytic reduction (SCR) of NO with NH₃ at around 200 °C and resistant to SO₂ deactivation. To elucidate its SCR mechanism, adsorption and oxidation of NH₃ over V₂O₅/AC are studied in this paper using TG, MS and DRIFTS techniques. It is found that the adsorption and oxidation of NH₃ take place mainly at VO bond of V₂O₅. A higher V₂O₅ loading results in more NH₃ adsorption on the catalyst. V₂O₅ contains both Brnsted and Lewis acid sites; NH₄⁺ on Brnsted acid sites is less stable and easier to be oxidized than NH₃ on Lewis acid sites. Gaseous O₂ promotes interaction of NH₃ with AC and oxidation of NH₃ over V₂O₅/AC. NH₃ is oxidized into NH₂ and acylamide structures and then to isocyanate species, which is an intermediate for N₂ formation.     

Selective oxidation of methanol to dimethoxymethane over acid-modified V2O5/TiO2 catalysts

Selective oxidation of methanol to dimethoxymethane (DMM) was conducted in a fixed-bed reactor over an acid-modified V₂O₅/TiO₂ catalyst. The influence of the acid modification on its structure, redox and acidic properties, and catalytic performance for methanol oxidation were investigated. The results indicated that the content of vanadia in the catalyst exhibits a vital influence on the dispersion of vanadium species, while the acid modification can enhance its surface acidity. Proper amounts of the acid (W() = 15%) and V₂O₅ (W(V₂O₅) = 15%) components loaded in the acid-modified V₂O₅/TiO₂ catalyst are able to build a bi-functional circumstance that is favorable for the formation of DMM with high activity and selectivity. As a result, for the selective oxidation of methanol, the H₂SO₄-modified V₂O₅/TiO₂ catalyst gives a much higher DMM yield at 150 °C than the unmodified one.     

Effects of electrolyte in dye-sensitized solar cells and evaluation by impedance spectroscopy

Effects of the electrolyte of DSCs on impedance spectra were evaluated by changing concentration of redox couple, viscosity, and additives to electrolyte. The relation with current-voltage characteristics (I-V characteristics) was investigated. In many cases, the impedance component attributed to charge transfer at TiO₂|electrolyte interface demonstrated strong relation with the I-V characteristics. The recombination of electrons in TiO₂ with I₃⁻ in electrolyte was a key factor in determining performance of DSCs. To evaluate the effect of I₃⁻, diffusion-limiting current in the electrolyte for various viscosities was evaluated by cyclic voltammetry. When the short circuit current (SCC) was almost equal to the diffusion-limiting current, strong influence of the diffusion coefficient on the impedance spectra was observed: impedance arcs were enlarged as the diffusion coefficient was decreased. On the other hand, when the diffusion-limiting current was larger than the SCC, photo-excitation and electron injection processes became dominating factors in the DSCs performance. The SCC was regulated by the charge recombination process at TiO₂|electrolyte interface, and thus the impedance component ω₃ was related to the performance in such condition.     

On the some electrical properties of the non-ideal PPy/p-Si/Al structure

The electrical analysis of the PPy/p-Si structure has been investigated by means of I-V, C-V and C-f measurements. The diode ideality factor and the barrier height have been obtained to be n=1.78 and Φ_b=0.69 eV by applying a thermionic emission theory, respectively. At high current densities in the forward direction, the series resistance effect has been observed. In general, the barrier height obtained from C-V data is greater than obtained from the I-V. This has been explained by introducing a spatial distribution of barrier heights (BHs) due to barrier height inhomogeneities that present at the PPy/p-Si interface. The C-f measurements of the structure have been performed at various biases and it has been seen that they have a good agreement between experimental and theoretical values. The interface state density N_ss and relaxation time τ of the structure have been determined from the C-f characteristics.