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.     

Glassy carbon electrodes modified with a film of nanodiamond-graphite/chitosan: Application to the highly sensitive electrochemical determination of Azathioprine

A novel modified glassy carbon electrode with a film of nanodiamond-graphite/chitosan is constructed and used for the sensitive voltammetric determination of azathioprine (Aza). The surface morphology and thickness of the film modifier are characterized using atomic force microscopy. The electrochemical response characteristics of the electrode toward Aza are investigated by means of cyclic voltammetry. The modified electrode showed an efficient catalytic role for the electrochemical reduction of Aza, leading to a remarkable decrease in reduction overpotential and enhancement of the kinetics of the electrode reaction with a significant increase of peak current. The effects of experimental variables, such as the deposited amount of modifier suspension, the pH of the supporting electrolyte, the accumulation potential and time were investigated. Under optimal conditions, the modified electrode showed a wide linear response to the concentration of Aza in the range of 0.2-100 μM with a detection limit of 65 nM. The prepared modified electrode showed several advantages: simple preparation method, high stability and uniformity in the composite film, high sensitivity, excellent catalytic activity in physiological conditions and good reproducibility. The modified electrode can be successfully applied to the accurate determination of trace amounts of Aza in pharmaceutical and clinical preparations.     

Nanoflakes of the cobaltous oxide, CoO: Synthesis and characterization

Nanoflakes of the cobaltous oxide as a thin film were deposited from a 100 mM cobalt (II) nitrate solution potentiostatically at −1000 mV (vs. Ag/AgCl) onto a platinum electrode surface. Surface morphology of the cobaltous oxide was studied by surface microscopy techniques (SEM, AFM and STM) and the electrochemical behavior was evaluated in alkaline solution using cyclic voltammetry and electrochemical impedance spectroscopy. Using cyclic voltammetry, the electron-transfer coefficient and the apparent charge-transfer rate constant of various redox transitions were determined. The cobaltous oxide electrode represented prominent electrocatalytic activity toward the mediated electrooxidation of ascorbic acid, glucose and methanol. In the Nyquist diagrams, different time constants appeared with relation to different physicochemical processes.     

染料敏化太阳能电池Pt/NiP/ITO对电极的制备和性能

在ITO导电玻璃表面化学镀NiP合金薄膜,然后电化学沉积Pt纳米粒子,形成染料敏化太阳能电池Pt/NiP/ITO对电极。优化了化学镀NiP合金的工艺条件;研究了NiP的结构和铂载量对Pt/NiP/ITO电极形貌和催化活性的影响。采用原子力显微镜分析Pt/NiP/ITO电极的表面形貌;采用循环伏安法、电化学交流阻抗法表征其电化学性能;采用单体DSSC的光电流–电压曲线表征其光伏性能。测试结果表明,在ITO基体上化学镀NiP合金,提高了电极的导电性和光反射能力,改善了电极表面Pt粒子的分布,使电池的短路电流密度和光电转化效率分别提高了4%和11%。     

Electrocatalytic oxidation of methanol on Cu modified polyaniline electrode in alkaline medium

Electrolytically deposited Cu on polyaniline film covered Pt substrate (Cu/PANI/Pt) is used as anode for the electrooxidation of methanol in alkaline medium. The electrochemical behavior and electrocatalytic activity of the electrode were characterized using cyclic voltammetry, impedance spectroscopy, chronomethods, rotating disc voltammetry and polarization studies. The morphology and composition of the modified film were obtained using SEM and EDAX techniques. The electrooxidation of methanol in NaOH is found to be more efficient on Cu/PANI/Pt than on bare Cu (Cu), electrodeposited Cu on Cu (Cu/Cu) and electrodeposited Cu on Pt (Cu/Pt) substrates. Partial chemical displacement of dispersed Cu on PANI with Pt or Pd further improved its performance towards methanol oxidation.     

A novel hydrazine electrochemical sensor based on a zirconium hexacyanoferrate film-bimetallic Au–Pt inorganic–organic hybrid nanocomposite onto glassy carbon-modified electrode

This work describes the electrochemical behavior of zirconium hexacyanoferrate (ZrHCF) film immobilized on the surface of bimetallic Au–Pt inorganic–organic hybrid nanocomposite glassy carbon electrode and its electrocatalytic activity toward the oxidation of hydrazine. The electrode possesses a three-dimensional (3D) porous network nano architecture (NFs). The surface structure and composition of the sensor was characterized by scanning electron microscopy (SEM). Electrocatalytic oxidation of hydrazine on the surface of modified electrode was investigated with cyclic voltammetry and chronoamperometry methods and the results showed that the ZrHCF film displays excellent electrochemical catalytic activities toward hydrazine oxidation. The modified electrode indicated reproducible behavior and high level of stability during the electrochemical experiments.     

Electrochemical synthesis and characterization of poly-2-aminothiazole

2-Aminothiazole (2AT) was electrochemically polymerized on a Pt electrode using cyclic voltammetry (CV) technique from 0.01 M monomer containing 0.3 M ammonium oxalate solution. The high quality poly-2-aminothiazole (pAT) films with a light-brownish color were obtained on the Pt surface. The electrochemical behavior of the pAT-coated Pt electrode (Pt/pAT) was investigated in monomer-free 0.3 M ammonium oxalate solution by CV technique. The chemical structure characterization was investigated by UV–vis spectroscopy (UV–vis) and Fourier transform infrared spectroscopy (FTIR) techniques. The surface morphology of the polymer film was examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface morphology studies showed that, a homogeneous and compact film was formed on the Pt surface. Further, thermogravimetric analysis (TGA), differential thermal analysis (DTA) and differential scanning calorimetry (DSC) techniques were used to investigate the thermal properties of the polymer film. It was found that the thermal stability of the pAT film is relatively high. The solubility of the pAT was tested in common organic solvents as well as in acidic and basic solutions.     

Synthesis and characterization of poly(aniline) and poly(o-anisidine) films in sulphamic acid solution and their anticorrosion properties

Poly(o-anisidine) (POA) and polyaniline (PANI) coatings were synthesized on platinum (Pt) surface and stainless steel (SS) in monomer containing 0.50 M sulphamic acid (SA) solution by means of cyclic voltammetry (CV) technique. Meanwhile, poly(o-anisidine) film was also deposited with a different scan rate on SS electrode. The behaviour of PANI and POA films obtained on stainless steel examined by CV was different from the one obtained for PANI and POA on Pt electrode. The corrosion performances of PANI and POA coatings in 3.5% NaCl solution were investigated with anodic polarization technique and electrochemical impedance spectroscopy (EIS). EIS measurements verified the effect of monomers and that of scan rate on corrosion inhibition of coatings on SS electrode. The results showed that POA film synthesized at low scan rate exhibited an effective anticorrosive property on SS electrode. POA synthesized at low scan rate and PANI coatings provided a remarkable anodic protection to SS substrate for longer exposure time than the one observed for POA coating produced at high scan rate as well as that of bare SS electrode.     

Electrocatalytic reduction of nitrite on tetraruthenated metalloporphyrins/Nafion glassy carbon modified electrode

This paper describes the electrochemical reduction of nitrite ion in neutral aqueous solution mediated by tetraruthenated metalloporphyrins (Co(II), Ni(II) and Zn(II)) electrostatically assembled onto a Nafion film previously adsorbed on glassy carbon or ITO electrodes. Scanning electron microscope (SEM-EDX) and transmission electron microscopy (TEM) results have shown that on ITO electrodes the macrocycles forms multiple layers with a disordered stacking orientation over the Nafion film occupying hydrophobic and hydrophilic sites in the polyelectrolyte. Atomic force microscopy (AFM) results demonstrated that the Nafion film is 35 nm thick and tetraruthenated metalloporphyrins layers 190 nm thick presenting a thin but compacted morphology. Scanning electrochemical microscopy (SECM) images shows that the Co(II) tetraruthenated porphyrins/Nf/GC modified electrode is more electrochemically active than their Ni and Zn analogues.These modified electrodes are able to reduce nitrite at −660 mV showing enhanced reduction current and a decrease in the required overpotential compared to bare glassy carbon electrode. Controlled potential electrolysis experiments verify the production of ammonia, hydrazine and hydroxylamine at potentials where reduction of solvent is plausible demonstrating some selectivity toward the nitrite ion. Rotating disc electrode voltammetry shows that the factor that governs the kinetics of nitrite reduction is the charge propagation in the film.     

The electrocatalytic oxidation of ascorbic acid on polyaniline film synthesized in the presence of β-naphthalenesulfonic acid

Polyaniline-β-naphthalenesulfonic acid composite film on platinum electrode surface has been synthesized via the electrochemical polymerization of aniline in the presence of β-naphthalenesulfonic acid (NSA). FT-IR, UV-vis and electrochemical characterization indicate the formation of the doped polyaniline. Further investigations found that the polyaniline (PAN) doped with NSA extended the electroactivity of PAN in neutral and even in alkaline media. The PAN-NSA composite film coated platinum electrodes are shown to be good electrocatalytic surfaces for the oxidation of ascorbic acid (AA) in phosphate buffer solution (PBS) of pH 7.0. The anode peak potential of AA shifts from 0.62 V at bare platinum electrode to 0.34 V at the PAN-NSA composite modified platinum electrode with greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5-60 mM using cyclic voltammetry. The kinetics of the catalytic reaction is investigated using rotating disk electrode (RDE) voltammetry, cyclic voltammetry and chronoamperometry. The results are explained using the theory of electrocatalytic reactions at chemically modified electrodes. The PAN-NSA composite film on the electrode surface shows good reproducibility and stability.     

Sputtered electrocatalysts for PEM electrochemical energy converters

The research reports on the electrocatalytic properties of IrO_x, Pt, and composite IrO_x-Pt-IrO_x thin films prepared by physical vacuum deposition technique of dc magnetron sputtering. The efficiency toward the oxygen evolution in aqueous solutions and in a laboratory electrolyser with polymer proton conductive electrolyte has been investigated using the conventional electrochemical methods of cyclic voltammetry and steady state polarisation curves. The sputtered films have demonstrated excellent catalytic properties, mechanical stability, and high corrosion resistance under intensive oxygen evolution. The best performance (anodic current density of 0.84 A cm⁻² at potential of 1.8 V) has shown the IrO_x film with loading of 0.2 mg cm⁻². Some data on the catalytic activity toward oxygen reduction reaction in aerated 0.5 M H₂SO₄ solution and the possibility to use the method of magnetron sputtering for preparation of cost effective composite catalytic films with bifunctional properties are also presented and discussed.     

Electrochemical characteristics of dopamine oxidation at palladium hexacyanoferrate film, electroless plated on aluminum electrode

A novel electrode material was obtained at an aluminum electrode (Al) by a simple electroless method including two consecutive procedures: (i) the electroless deposition of metallic palladium on the Al electrode surface from PdCl₂ + 25% ammonia solution and (ii) the chemical transformation of deposited palladium to the palladium hexacyanoferrate (PdHCF) films in a solution containing 0.5 M K₃[Fe(CN)₆]. The modified Al electrode demonstrated a well-behaved redox couple due to the redox reaction of the PdHCF film. The PdHCF film showed an excellent electrocatalytic activity toward the oxidation of dopamine (DA). The effect of solution pH on the voltammetric response of DA has been investigated. A linear calibration graph was obtained over the DA concentration range 2-51 mM. The rate constant k and transfer coefficient α for the catalytic reaction and the diffusion coefficient of DA in the solution D, were found to be 4.67 × 10² M⁻¹ s⁻¹, 0.63 and 2.5 × 10⁻⁶ cm² s⁻¹, respectively. The interference of ascorbic acid was investigated and greatly reduced using a thin film of Nafion on the modified electrode. The modified electrode indicated reproducible behavior and a high level stability during electrochemical experiments, making it particularly suitable for the analytical purposes.     

Enhanced performance of a dye-sensitized solar cell with an electrodeposited-platinum counter electrode

A counter electrode was prepared for a dye-sensitized solar cell (DSSC) through electrochemical deposition of mesoporous platinum on fluorine-doped tin oxide glass in the presence of a structure-directing nonionic surfactant, octaethylene glycol monohexadecyl ether (C₁₆EO₈). The DSSC fabricated with the electrochemically deposited Pt (ED-Pt) counter electrode rendered a higher solar-to-electricity conversion efficiency of 7.6%, compared with approximately 6.4% of the cells fabricated with the sputter-deposited or most commonly-employed thermal deposited Pt counter electrodes. This enhanced efficiency is attributed to the higher short-circuit photocurrent arising from the increases in the active surface area and light reflection as well as the decrease in the sheet resistance of the ED-Pt film, relative to those of the Pt films prepared by the other two deposition methods. The sputter-deposited Pt film yielded almost the same photovoltaic characteristics as the thermal deposited Pt film. The Pt films were characterized by FE-SEM, AFM, cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy, sheet resistance measurements, adhesion tests, and light reflection tests.     

Sputtered iridium oxide films as electrocatalysts for water splitting via PEM electrolysis

Thin films of iridium oxide deposited by reactive magnetron sputtering have been investigated as catalysts for electrochemical water splitting in a polymer electrolyte membrane (PEM) cell. The sputtered films possess excellent mechanical stability and corrosion resistance at the high anodic potentials where oxygen evolution takes place. Their catalytic activity has been assessed using the conventional electrochemical methods of cyclovoltammetry and steady state polarisation techniques. A morphology factor assessing the catalyst active surface for a series of sputtered samples with varying thickness/loading has been determined and correlated to the catalytic efficiency. It has been proven that iridium oxide is a very efficient catalyst for oxygen evolution reaction (OER). The best performance with anodic current density of 0.3 A cm⁻² at potential of 1.55 V (versus RHE) has shown the 500 nm thick film containing 0.2 mg cm⁻² catalyst. The results obtained have also demonstrated the advantages of the reactive magnetron sputtering as simple and reliable method for deposition of efficient and cost effective catalysts for PEM electrolysis application.     

Electrochemical characteristics of amophous carbon coated silicon electrodes

The properties of carbon films deposited by the radio frequency plasma sputtering of a fullerene C₆₀ target were investigated to elucidate the dependence on the plasma power. A radio frequency argon plasma power ranging from 50 to 300W at a pressure of 1.3 Pa was applied for sputtering. This corresponds to a self-bias potential on the target ranging from −95 to −250 V and a maximum argon ion energy ranging from 240 to 575 eV. The analysis of the G and D peaks in the Raman spectra shows that the films are similar to tetragonal hydrogenated amorphous carbon annealed at 600–1,000 °C. The electron band structure of the carbon films deposited by the sputtering of C₆₀ depends on the plasma power. The coating effect of these carbon films on the capacity performance of the silicon film electrode of lithium secondary batteries was significant in our experimental range. An electrochemical test revealed that such carbon thin film on the silicon electrode plays an important role in mitigating the capacity fading during the charge and discharge processes. The test revealed that the film formed at a plasma power of 300 W is the most effective.     

Composite electrodes consisting of platinum particles and polyaniline nanowires as electrocatalysts for methanol oxidation

Polyaniline (PANI) with nanowire (PANI‐(NW)) network structure (mean diameter 10–20 nm) was successfully deposited on a stainless steel (SS) electrode by a galvanostatic process. Platinum particles were deposited into the PANI nanowire network structure to result the PANI(NW)‐Pt composite electrode. The PANI(NW)‐Pt electrode was used as electrocatalysts for the electrochemical oxidation of methanol. The PANI nanowires and PANI(NW)‐Pt nanocomposite were characterized by scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), and UV–vis absorption spectroscopy. Nanowire morphology with an average diameter of 10–20 nm could be seen from scanning electron micrograph. Small amount (70 mμm) of spherical Pt particles could be deposited into the PANI(NW). Catalytic activity for the oxidation of methanol was studied by using cyclic voltammetry (CV). For comparative purposes, bulk Pt (deposited Pt on SS) and PANI nanowires based electrodes were tested. The PANI(NW)‐Pt nanocomposite electrode exhibited excellent catalytic activity for the electrooxidation of methanol in comparison to bulk Pt electrodes, which reveals that the PANI(NW)‐Pt nanocomposite electrodeis more promising for application in electrocatalyst as a support material. POLYM. COMPOS., 28:650–656, 2007. © 2007 Society of Plastics Engineers     

Kinetics of hydrogen oxidation reaction on Nafion-coated Pt/C electrodes under high overpotentials

The influences of the Nafion film thickness and Pt loading on the kinetics of the hydrogen oxidation reaction on Nafion-coated 20 wt% Pt/C electrodes immersed in 0.5 M H₂SO₄ were investigated using a rotating disk electrode configuration. The coating of a Nafion film (8 μm) had a negligible effect on the electrochemical surface area of an electrode. The kinetic parameters were estimated at an overpotential of 0.4 V; the values obtained were shown to vary with the method of data treatment. The diffusional resistance for H₂ in the Nafion film was negligible when the film was thinner than 0.2 μm. The permeability of H₂ in the Nafion film ranged from 2.4 × 10⁻⁵ to 4.8 × 10⁻⁵ mM cm²/s. The error analysis demonstrated that the apparent kinetic current estimated was resulted from experimental errors, instead of resulting from a chemical process as proposed by some previous investigators.     

The catalysts supported on metallized electrospun polyacrylonitrile fibrous mats for methanol oxidation

Polyacrylonitrile nanofibrous mats coated with continuous thin gold films (Au-PAN) have been fabricated by combining the electrospinning and electroless plating techniques. The Pt particles are electrodeposited on the Au-PAN fibers surface by multi-cycle CV method, and the Au-PAN decorated with Pt (Pt/Au-PAN) shows higher activity toward methanol electro-oxidation. The catalytic peak current for methanol oxidation on the optimum Pt/Au-PAN electrode can reach about 450 mA mg⁻¹ Pt which is much larger than the catalytic peak current for methanol oxidation (118.4 mA mg⁻¹ Pt) on the electrode prepared by loading commercial Pt/C on Au-PAN (Pt/C/Au-PAN). Further experiments reveal that the Pt/Au-PAN electrodes exhibit better stability and smaller charge transfer resistance than Pt/C/Au-PAN electrodes, which indicates that the Au-PAN may be developed as supporting material for catalyst. The microscopy images of the electrodes show that the Pt particles deposited on Au-PAN conglomerate into larger particles, and that the Pt/C catalyst loaded on the Au-PAN also exhibits conglomeration after stability test. The hydrogen adsorption-desorption experiments indicate that the electrochemical surface area of the Pt particles for the both kinds of electrodes has decreased after stability test.     

Studies on electrochemical properties of MWNTs-Nafion composite films based on the redox behavior of incorporated Eu by voltammetry and electrochemical impedance spectroscopy

MWNTs can be conveniently dispersed in Nafion solution on the basis of the special interactions between the sidewall of MWNTs and the hydrophobic domains of Nafion. Casting of the resulting mixture on electrode surfaces produced uniform composite films having wide electroanalytical applications. In this work, the electrochemical properties of the MWNTs-Nafion composite film on a glassy carbon electrode were systematically investigated by various electrochemical methods using incorporated europium(III) ions (Eu³⁺) as the probe. The voltammetric studies showed that the increase of MWNTs concentration in the composite film could effectively improve the redox currents of Eu³⁺ and reduce the peak separation, whereas the increase of Nafion concentration generally increased both the redox currents and the peak separation. These results suggested the different roles of MWNTs and Nafion in the composite films. The electrochemical impedance spectroscopic (EIS) investigations showed that MWNTs mainly contributed to the charge transfer and mass transfer processes of the composite film through the increases of the electrode/electrolyte interfacial area and the film porosity while Nafion generally dominated the mass transport from the solution into the film via ion exchange. The potential application of the sensitive response of Eu³⁺ at the MWNTs-Nafion composite film in electroanalytical chemistry was evaluated. In the range of 0.04-100 μM, the concentration of Eu³⁺ showed excellent linear relationships with the differential pulse voltammetric response with a low detection limit of 10 nM (S/N = 3) for 60 s accumulation at −0.1 V.     

Graphene aerogels as a highly efficient counter electrode material for dye-sensitized solar cells

Graphene aerogels (GAs) prepared with an organic sol–gel process, possessing a high specific surface area of 814 m²/g and a high electric conductivity of 850 S/m, are applied as a counter electrode material for dye-sensitized solar cells (DSSCs). The performance of the GA as the counter electrode material is found to be dependent on its film thickness, with thicker films offering more surface areas for the involved catalytic reduction reaction but at the same time increasing the charge and mass transport resistances. At an optimum GA film thickness of 4.9 μm, a power conversion efficiency of 96% of that achieved with a Pt counter electrode based DSSC is obtained. In addition, a thinner GA film of 1.7 μm, when loaded with Pt of 1 mol% through a photo-reduction process, achieves a power conversion efficiency of 98% of that obtained with a Pt counter electrode based DSSC. The excellent performances of the GA-based counter electrodes are manifested with electrochemical impedance analyses and cyclic voltammetry based catalytic activity analyses.