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1.
Some ternary ferrites with molecular formula, CoFe2−xCrxO4 (0≤x≤1.0) have been synthesized at 70 °C by a precipitation method and were transformed into the film form at the pretreated Ni support (1.5×1.0 cm2) using an oxide-slurry painting technique. The study showed that Cr-substitution from 0.2 to 1.0 mol increased the electrocatalytic activity of the oxide towards the oxygen evolution reaction (OER), the optimum improvement in apparent electrocatalytic activity being with 0.8 mol Cr. At E=600 mV versus Hg/HgO in 1 M KOH (25 °C), the apparent oxygen evolution current density (ja) with the catalyst, CoFe1.2Cr0.8O4, was ∼80 times greater than that observed with the base oxide (i.e. CoFe2O4). The OER on Cr-substituted oxides showed two Tafel slopes, one (b=42±1 mV per decade) at low overpotential and the other (b=66±6 mV per decade) at higher potential. The reaction order with respect to OH concentration was ∼1.3±0.1 for each electrocatalyst. The thermodynamic parameters for the OER, namely, standard apparent electrochemical enthalpy of activation (ΔH°el#), standard enthalpy of activation (ΔH°#) and standard entropy of activation (ΔS°#) have also been determined. It was observed that values of the ΔH°el# and ΔH°# decreased with Cr-substitution in the CoFe2O4 lattice; the decrement, however, being the greatest with 0.8 mol Cr. The ΔS°# values were largely negative varying between ∼−61 and −126 J deg−1 mol−1.  相似文献   

2.
Hao Yu 《Electrochimica acta》2007,52(13):4403-4410
The gallium hexacyanoferrate (GaHCF) was synthesized chemically and characterized by FTIR technique. Its electrochemical behavior was carefully investigated by fabricating a GaHCF modified carbon paste electrode in various supporting electrolyte. The experimental results showed that in KNO3, K2SO4, KCl and other supporting electrolyte, GaHCF yielded one pair of ill-defined redox waves with a formal potential of 0.9 V (versus SCE). In 0.050 mol L−1 phosphate buffer solution (PBS, pH 6.8), however, GaHCF yielded one pair of well-defined redox peaks with a formal potential of 0.222 V. Furthermore, this modified electrode exhibited a high electrocatalytic activity toward the reduction of H2O2 in pH 6.8 PBS, with over-potential dramatically lower than that of on the bare carbon paste electrode. Amperometry was used for the determination of H2O2, under the optimal conditions, a linear dependence of the catalytic current versus H2O2 concentration was obtained in the range of 4.9 × 10−6 to 4.0 × 10−4 mol L−1 with a detection limit of 1 × 10−6 mol L−1 when the signal-to-noise ratio was 3, and a sensitivity of 27.9 μA mM−1 (correlation coefficient of 0.997). Chronoamperometry was used to conveniently determine the diffusion coefficient of H2O2 in the solution.  相似文献   

3.
K.M. Shaju 《Electrochimica acta》2003,48(11):1505-1514
Layered Li(Ni1/2Mn1/2)O2 was prepared by the solution and mixed hydroxide methods, characterised by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and studied by cyclic voltammetry (CV) and charge discharge cycling in CC and CCCV modes at room temperature (r.t.) and at 50 °C. The XPS studies show about 8% of Ni3+ and Mn3+ ions are present in Li(Ni2+1/2Mn1/24+)O2 due to valency-degeneracy. The compound prepared at 950 °C, 12 h, solution method gives a second cycle discharge capacity of 150 mA h g−1 (2.5-4.4 V) at a specific current of 30 mA g−1 and retains 137 mA h g−1 at the end of 40 cycles. CV shows that the redox process at 3.7-4.0 V corresponds to Ni2+↔Ni4+ and clear indication of Mn3+/4+ couple was noted at 4.2-4.5 V. The observed capacity-fading (2.5-4.4 V) is shown to be contributed by the polarisation at the end of charging. The cathodic capacity is stable up to 40 cycles in the voltage window, 2.5-4.2 V both at room temperature and 50 °C.  相似文献   

4.
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, Em, 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.  相似文献   

5.
This work provides kinetic and transport parameters of Li-ion during its extraction/insertion into thin film LiNi0.5Mn1.5O4 free of binder and conductive additive. Thin films of LiNi0.5Mn1.5O4 (0.2 μm thick) were prepared on electronically conductive gold substrate utilizing the electrostatic spray deposition technique. High purity LiNi0.5Mn1.5O4 thin film electrodes were observed with cyclic voltammetry, to exhibit very sharp peaks, high reversibility, and absence of the 4 V signal related to the Mn3+/Mn4+ redox couple. The electrode subjected to 100 CV cycles of charge/discharge delivered a capacity of 155 mAh g−1 on the first cycle and sustained a good cycling behavior while retaining 91% of the initial capacity after 50 cycles. Kinetics and mass-transport of Li-ion extraction at LiNi0.5Mn1.5O4 thin film electrode were investigated by means of electrochemical impedance spectroscopy. The apparent chemical diffusion coefficient (Dapp) value determined from EIS measurements changed depending on the electrode potential in the range of 10−10-10−12 cm2 s−1. The Dapp profile shows two minimums at the potential values close to the peak potentials of the corresponding cyclic voltammogram.  相似文献   

6.
RuO2-based electrodes are generally known to be unstable for O2 evolution. In this paper, a stable type of RuO2-based electrode, Ti/RuO2-Sb2O5-SnO2, is demonstrated for O2 evolution. In the ternary oxide coating, RuO2 serves as the catalyst, SnO2 as the dispersing agent, and Sb2O5 as the dopant. The accelerated life test showed that the Ti/RuO2-Sb2O5-SnO2 electrode containing 12.2 molar percent of RuO2 nominally in the coating had a service life of 307 h in 3 M H2SO4 solution under a current density of 0.5 A cm−2 at 25 °C, which is more than 15 times longer than other types of RuO2-based electrodes. Instrumental analysis indicated that RuO2-Sb2O5-SnO2 was a solid solution with a compact structure, which contributed to the stable nature of the electrode.  相似文献   

7.
The stability of one material, Ti/CuxCo3−xO4, as anode and also cathode was investigated for electrolysis of alkaline aqueous solution. The electrodes were prepared by thermal decomposition method with x varied from 0 to 1.5. The accelerated life test illustrated that the electrodes with x = 0.3 nominally showed the best performance, with a total service life of 1080 h recorded in 1 M NaOH solution under alternating current direction at 1 A cm−2 and 35 °C. The effects of copper content in electrode coating were examined in terms of electrode stability, surface morphology, coating resistivity and coating compositions. The presence of Cu in the spinel structure of Co3O4 could significantly enhance the electrochemical and physicochemical properties. The trends of crystallographic properties and surface morphology have been analyzed systemically before, during and after the electrodes were employed in alkaline electrolysis. The oxygen evolution would lead to the consumption of the coating material and the progressive cracking of the coating. Along with hydrogen evolution, cobalt oxide could be reduced to metal Co and Co(OH)2 with particle sizes changed to smaller values in crystal and/or amorphous form at the cathode. The formation of Co is the key process for this electrode to serve as both anode and cathode. It is also the main reason leading to the eventual failure of the electrodes.  相似文献   

8.
In this work, bare and Ta-substituted Nb2O5 nanofibers are prepared by electrospinning followed by sintering at temperatures in the 800–1100 °C range for 1 h in air. Obtained bare and Ta-substituted Nb2O5 polymorphs are characterized by X-ray diffraction, scanning electron microscopy, density measurement, and Brunauer, Emmett and Teller surface area. Electrochemical properties are evaluated by cyclic voltammetry and galvanostatic techniques. Cycling performance of Nb2O5 structures prepared at temperature 800 °C, 900 °C, and 1100 °C shows following discharge capacity at the end of 10th cycle: 123, 140, and 164 (±3) mAh g−1, respectively, in the voltage range 1.2–3.0 V and at current rate of 150 mA g−1 (1.5 C rate). Heat treated composite electrode based on M-Nb2O5 (1100 °C) in argon atmosphere at 220 °C, shows an improved discharge capacity of 192 (±3) mAh g−1 at the end of 10th cycle. The discharge capacity of Ta-substituted Nb2O5 prepared at 900 °C and 1100 °C showed a reversible capacity of 150, 202 (±3) mAh g−1, respectively, in the voltage range 1.2–3.0 V and at current rate of 150 mA g−1. Anodic electrochemical properties of M-Nb2O5 deliver a reversible capacity of 382 (±5) mAh g−1 at the end of 25th cycle and Ta-substituted Nb2O5 prepared at 900 °C, 1000 °C and 1100 °C shows a reversible capacity of 205, 130 and 200 (±3) mAh g−1 (at 25th cycle) in the range, 0.005–2.6 V, at current rate of 100 mA g−1.  相似文献   

9.
Hydrogen evolution from 0.5 M H2SO4 on Ti electrodes coated with a RuxTi1−xO2 (x=0.04-0.5) layer has been studied by potentiostatic polarisation, cyclic voltammetry and ac-impedance spectroscopy. The results indicate that after a certain activation period the performance of such an electrode coating is comparable to platinum. The addition of small amounts of sodium molybdate increased the capacitance of the electrode and a reduction of the performance was observed. Increasing the temperature of the pure electrolyte from 20 to 75 °C caused an increase in the rate of the hydrogen evolution and in addition an increase of the electrode capacitance. The electrodes have been found to be rather tolerant to chloride and Fe2+ ions, and could hence be promising candidates as catalyst materials for solid polymer water electrolysis systems. From steady state measurements the Tafel slopes were found to change from −105 mV/decade for pure titanium to about −40 mV/decade for the (RuTi)O2 coated electrodes. The exchange current densities were calculated from the steady state curves, as well as from impedance data, to be about 10−4 A cm−2 after activation.  相似文献   

10.
A composite lithium battery electrode of LiMn2O4 in combination with a gel electrolyte (1 M LiBF4/24 wt% PMMA/1:1 EC:DEC) has been investigated by galvanostatic cycling experiments and electrochemical impedance spectroscopy (EIS) at various temperatures, i.e. −3<T<56 °C. For analysis of EIS data, a mathematical model taking into account local kinetics and potential distribution in the liquid phase within the porous electrode structure was used. Reasonable values of the double-layer capacitance, the exchange-current density and the solid phase diffusion were found as a function of temperature. The apparent activation energy of the charge-transfer (∼65 kJ mol−1), the solid phase transfer (∼45 kJ mol−1) and of the ionic bulk and effective conductance in the gel phase (∼34 kJ mol−1), respectively, were also determined. The kinetic results related to ambient temperature were compared to those obtained in the corresponding liquid electrolyte. The incorporated PMMA was found to reduce the ionic conductivity of the free electrolyte, and it was concluded that the presence of 24 wt% PMMA does not have a significant influence on the kinetic properties of LiMn2O4.  相似文献   

11.
Electrochemical behaviors of 2.5 V Li[Li1/3Ti5/3]O4 (LTO)/Li[Li0.1Al0.1Mn1.8]O4 (LAMO) cells for the first-generation 12 V lead-free battery were examined at −10, 25, and 55 °C. The LTO/LAMO cells showed the same rechargeable capacity in temperature ranging from −10 to 55 °C when the cells were examined at 0.5 mA cm−2 in cell potential ranging from 0 to 3.0 V. Capacity fading after 250 cycles was negligibly small at −10 °C. Rechargeable capacities, however, faded 5% at 25 °C and 15% at 55 °C after 250 cycles. In the discharged LTO/LAMO cell after 250 cycles at 55 °C, the state of charge (SOC) of the positive electrode was 16% while SOC of the negative electrode was 0%, indicated that the capacity fading was due to an imbalance in SOC between the positive and negative electrodes. To understand the progress of an imbalance in SOC, the LTO/LAMO cell with a lithium auxiliary electrode was fabricated and examined at 55 °C for 400 cycles, and the possible origin of capacity fading was discussed.  相似文献   

12.
[Os(bpy)3]3[P2W18O62] has been synthesised and characterised by elemental analysis, spectroscopic (UV-vis, IR spectroscopy) and electrochemical techniques. In 0.1 M Bu4NPF6 DMSO the complex shows a series of redox couples associated with the Os3+/2+ and bipyridine ligands of the cationic [Os(bpy)3]2+ moiety and the tungsten-oxo framework of the associated Dawson parent heteropolyanion, [P2W18O62]6−. At this electrolyte concentration, the Os3+ redox form of the complex was seen to adsorb onto the electrode surface. When the electrolyte concentration is lowered to 0.01 M Bu4NPF6 in addition to the Os3+/2+ redox couple, the redox process associated with the [P2W18O62]8−/7− couple also exhibited properties indicating surface based processes were present. Electroactive films of the complex were formed on carbon macroelectrodes by the redox switching of the transition metal within the complex. Voltammetric investigations into the film's behaviour in a range of buffer solutions (pH 2.0, 4.5 and 7.0) were performed. The films were found to possess better stability in acidic pH and the same pH dependence for the tungsten-oxo framework of the heteropolyanions as in solution. Solid state electrochemical measurements on mechanically attached microparticles of the complex were performed, with the effect of both the nature and concentration of the aqueous electrolyte on this behaviour being investigated. Upon redox switching between the Os2+/3+ redox states, there is an associated insertion/expulsion of anions from/to the solution phase. Scanning electron micrographs of these solid state films were attained before and after redox cycling.  相似文献   

13.
The modification of activated carbon fibres prepared from a commercial textile acrylic fibre into materials with monolithic shape using phenolic resin as binder was studied. The molecular sieving properties for the gas separations CO2/CH4 and O2/N2 were evaluated from the gas uptake volume and selectivity at 100 s contact time taken from the kinetic adsorption curves of the individual gases. The pseudo-first order rate constant was also determined by the application of the LDF model. The samples produced show high CO2 and O2 rates of adsorption, in the range 3-35 × 10−3 s−1, and in most cases null or very low adsorption of CH4 and N2 which make them very promising samples to use in PSA systems, or similar. Although the selectivity was very high, the adsorption capacity was low in certain cases. However, the gas uptake in two samples reached 23 cm3 g−1 for CO2 and 5 cm3 g−1 for O2, which can be considered very good. The materials were heat-treated using a microwave furnace, which is a novel and more economic method, when compared with conventional furnaces, to improve the molecular sieves properties.  相似文献   

14.
In this work, we examined the electrochemical behaviour of lithium ion batteries containing lithium iron phosphate as the positive electrode and systems based on Li-Al or Li-Ti-O as the negative electrode. These two systems differ in their potential versus the redox couple Li+/Li and in their morphological changes upon lithium insertion/deinsertion. Under relatively slow charge/discharge regimes, the lithium-aluminium alloys were found to deliver energies as high as 438 Wh kg−1 but could withstand only a few cycles before crumbling, which precludes their use as negative electrodes. Negative electrodes consisting solely of aluminium performed even worse. However, an electrode made from a material with zero-strain associated to lithium introduction/removal such as a lithium titanate spinel exhibited good performance that was slightly dependent on the current rate used. The Li4Ti5O12/LiFePO4 cell provided capacities as high as 150 mAh g−1 under C-rate in the 100th cycle.  相似文献   

15.
In this work, SiO2/Sb2O3 prepared by the sol-gel processing method, having a specific surface area, SBET, of 790 m2 g−1, an average pore diameter of 1.9 nm and 4.7 wt.% of Sb, was used as substrate base for immobilization of the 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphine ion. Cobalt(II) ion was inserted into the porphyrin ring with a yield of complex bonded to the substrate surface of 59.4 μ mol g−1. A carbon paste electrode of this material was used to study, by linear sweeping voltammetric and chronoamperometric techniques, the electrocatalytic reduction of dissolved oxygen. The reduction, at the electrode solid-solution interface, occurred at −0.25 V versus SCE in 1.0 mol l−1 KCl solution, pH 5.5, by a four electron mechanism. The electrode response was invariant under various oxidation-reduction cycles showing that the system is chemically very stable. Such characteristics allowed the study of the electrode response towards various dissolved oxygen concentrations using the chronoamperometry technique. The cathodic peak current intensities plotted against O2 concentrations, between 1.0 and 12.8 mg l−1, showed a linear correlation. The electrode response time was very fast, i.e. about 1 s. This study was extended using the electrode to determine the concentration of dissolved oxygen in sea water samples.  相似文献   

16.
In this work, two layered double hydroxides, Zn2Cr–ABTS and Zn2Al–Fe(CN)6 LDH, have been synthesized and characterized by X ray diffraction and FTIR spectroscopy to confirm the intercalation of redox anions between inorganic layers. These redox active hybrid materials have been used to electrically connect laccase (Lac) and glucose oxidase (GOx) in biofuel cell devices. Co-immobilization of hybrid LDH and enzymes has been performed by entrapment in electropolymerized films of polypyrrole deposited on porous carbon tubular electrodes. Lac/Zn2Cr–ABTS cathodic electrode allows the electro-enzymatic reduction of O2, whereas the anodic electrode GOx/Zn2Al–FeIII(CN)6was used for the electro-enzymatic oxidation of glucose. With a two compartment configuration, a maximum power density of 45 μW cm−2was obtained at 0.2 V.  相似文献   

17.
Direct electrochemistry of hemoglobin can be performed in acidic and basic aqueous solutions in the pH range 1-13, using stable, electrochemically active films deposited on a didodecyldimethylammonium bromide (DDAB) modified glassy carbon electrode. Films can also be produced on gold, platinum, and transparent semiconductor tin oxide electrodes. Hemoglobin/DDAB films exhibit one, two, and three redox couples when transferred to strong acidic, weak acidic and weak basic, and strong basic aqueous solutions, respectively. These redox couples, and their formal potentials, were found to be pH dependent. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ deposition of DDAB on gold disc electrodes and hemoglobin deposition on DDAB film modified electrodes. A hemoglobin/DDAB/GC modified electrode is electrocatalytically reduction active for oxygen and H2O2, and electrocatalytically oxidation active for S2O42− through the Fe(III)/Fe(II) redox couple. In the electrocatalytic reduction of S4O62−, S2O42−, and SO32−, and the dithio compounds of 2,2′-dithiosalicylic acid and 1,2-dithiolane-3-pentanoic acid, the electrocatalytic current develops from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in neutral and weakly basic aqueous solutions. Hemoglobin/DDAB/GC modified electrodes are electrocatalytically reduction active for trichloroacetic acid in strong acidic buffered aqueous solutions through the Fe(III)/Fe(II) redox couple. However, the electrocatalytic current developed from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in weak acidic and basic aqueous solutions. The electrocatalytic properties were investigated using the rotating ring-disk electrode method.  相似文献   

18.
The microwave dielectric properties of Sm(Mg0.5Ti0.5)O3 incorporated with various amount of Bi2O3 and B2O3 additives have been investigated systematically. In this study, both Bi2O3 and B2O3 additives acting as a sintering aid can effectively lower the sintering temperature from 1550 °C to 1300 °C. The ionic radius of Bi3+ for a coordination number of 6 is 0.103 nm, whereas the ionic radius of B3+ is 0.027 nm. Clearly, the ionic radius of Bi3+ is greatly larger than one of B3+, which resulted in the specimens incorporated with Bi2O3 having larger lattice parameters and cell volume than those incorporated with B2O3. The experimental results show that no second phase was observed throughout the entire experiments. Depending on the interfacial tension, the liquid phase may penetrate the grain boundaries completely, in which case the grains will be separated from one another by a thin layer as shown in Sm(Mg0.5Ti0.5)O3 ceramics incorporated with Bi2O3. Whereas, in Sm(Mg0.5Ti0.5)O3 ceramics incorporated with B2O3, the volume fraction of liquid is high, the grains may dissolve into the liquid phase, and rapidly rearrange, in which case contact points between agglomerates will be dissolved due to their higher solubility in the liquid, leading plate-like shape microstructure.A dielectric constant (?r) of 29.3, a high Q × f value of 26,335 GHz (at 8.84 GHz), and a τf of −32.5 ppm/°C can be obtained for Sm(Mg0.5Ti0.5)O3 ceramics incorporated with 10 mol% Bi2O3 sintered at 1300 °C. While Sm(Mg0.5Ti0.5)O3 ceramics incorporated with 5 mol% B2O3 can effectively lower temperature coefficient of resonant frequency, which value is −21.6 ppm/°C. The Sm(Mg0.5Ti0.5)O3 ceramic incorporated with heavily Bi2O3 and B2O3 additives exhibits a substantial reduction in temperature (∼250 °C) and compatible dielectric properties in comparison with that of an un-doped one. This implied that this ceramic is suitable for miniaturization in the application of dielectric resonators and filters by being appropriately incorporated with a sintering aid.  相似文献   

19.
The ac response of polyaniline thin films on platinum electrodes was measured at different dc potentials during the CO2 reduction in methanol/LiClO4 electrolyte with a small amount of 0.5 M H2SO4. The complex capacitance curves were simulated and the data obtained were used to calculate kinetic parameters, based on the assumption that the thermodynamic potential E0 is in the region of −0.2-−0.1 V versus saturated calomel electrode (SCE). With E0=−0.2 V versus SCE and β=0.6, a j0 value of ca. 10−4 A cm−2 was found for the electroreduction of CO2 on the polyaniline electrode.  相似文献   

20.
Synthesis, electrochemical, and structural properties of LiNi0.8Co0.15Al0.05O2 cathodes prepared by TiO2 nanoparticles coating on a Ni0.8Co0.15Al0.05(OH)2 precursor have been investigated by the variation of coating concentration and annealing temperature. TiO2-coated cathodes showed that Ti elements were distributed throughout the particles. Among the coated cathodes, the 0.6 wt% TiO2-coated cathode prepared by annealing at 750 °C for 20 h exhibited the highest reversible capacity of 176 mAh g−1 and capacity retention of 92% after 40 cycles at a rate of 1C (=190 mA g−1). On the other hand, an uncoated cathode showed a reversible first discharge capacity of 186 mAh g−1 and the same capacity retention value to the TiO2-coated sample at a 1C rate. However, under a 1C rate cycling at 60 °C for 30 cycles, the uncoated sample showed a reversible capacity of 40 mAh g−1, while a TiO2-coated one showed 71 mAh g−1. This significant improvement of the coated sample was due to the formation of a possible solid solution between TiO2 and LiNi0.8Co0.15Al0.05O2. This effect was more evident upon annealing the charged sample while increasing the annealing temperature, and at 400 °C, the coated one showed a more suppressed formation of the NiO phase from the spinel LiNi2O4 phase than the uncoated sample.  相似文献   

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