Water in Sugar Electrolytes and Application to Electrodeposition of Superconducting Rhenium

A systematic electrochemical study is carried out on electrolytes with superhigh concentrations of fructose. The effect of fructose concentration on the viscosity and conductivity of electrolyte are determined and analyzed using Walden rule and the theory of rate process. The diffusion rates of proton and cupric cation are calculated from the peak current in cyclic voltammogram on stationary electrode and the limiting current on rotating electrodes. Raman spectroscopy is used to characterize the hydrogen bond network in water and the effect of fructose concentration on such network. Rhenium deposition with different fructose concentrations is studied on rotating disc electrodes. X-ray fluorescence, X-ray diffraction, and four point probe measurements at cryogenic temperature are used to study the deposition rate, crystallographic structure, and superconductivity of film, respectively.

Electrodeposition of Indium from an Ionic Liquid Investigated by In Situ Electrochemical XPS

The electrochemical behavior and electrodeposition of indium in an electrolyte composed of 0.1 mol/L InCl3 in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py1,4]TFSI) on a gold electrode were investigated. The cyclic voltammogram revealed several reduction and oxidation peaks, indicating a complex electrochemical behavior. In the cathodic regime, with the formation of an In-Au alloy, the reduction of In(III) to In(I) and of In(I) to In(0) takes place. In situ electrochemical X-ray photoelectron spectroscopy (XPS) was employed to investigate the reduction process by monitoring the oxidation states of the components during the cathodic polarization of 0.1 mol/L InCl3/[Py1,4]TFSI on a gold working electrode under ultra-high vacuum (UHV) conditions. The core electron binding energies of the IL components (C 1s, O 1s, F 1s, N 1s, and S 2p) shift almost linearly to more negative values as a function of the applied cell voltage. At −2.0 V versus Pt-quasi reference, In(I) was identified as the intermediate species during the reduction process. In the anodic regime, a strong increase in the pressure in the XPS chamber was recorded at a cell voltage of more than −0.5 V versus Pt quasi reference, which indicated, in addition to the oxidation reactions of In species, that the oxidation of Cl− occurs. Ex situ XPS and XRD results revealed the formation of metallic In and of an In-Au alloy.

Mathematical Modeling of Cyclic Voltammogram Curves of Copper Deposition

The manufacturing of interconnects and the packaging of integrated circuits are achieved with electrodeposition of copper or other metals. In order to increase the rate of deposition, especially for the large features in packaging, forced convection is provided with certain agitation mechanisms. Although this reduces deposition time, it leads to non-uniform mass transport within each feature and between different features. Special organic additives are used in the solution during the process in order to tune the nucleation and growth of metal, as well as to modify the deposition rate and improve the uniformity. A mathematical model to describe the behavior of organic additives in conjugation with fluid flow and features of various geometry and dimensions is very much desired to facilitate chemistry and process development. In order to achieve this, the physiochemical kinetics of additive and their influence on the Cu deposition rate need to be described precisely. This presentation focuses on a method to extract the kinetic parameters describing the combined effect of multiple additives during copper deposition using rotating disk electrode (RDE). The one-dimensional steady state convection-diffusion equation for each of the chemical species including copper is solved by a semi-analytical method for a range of potentials. The boundary conditions of these differential equations are coupled on the surface of the RDE through the surface coverage of the absorbed species. The steady state of surface coverage of the species represents a dynamic equilibrium of three key processes i.e., adsorption, desorption, and consumption (incorporation). When equilibrium is achieved, the net rate of adsorption and desorption becomes equal to the rate of consumption. At each value of potential, the surface coverage of the additives is solved. At first, the solution is obtained with only one species known as suppressor and it was found that in a specific range of voltage and kinetic parameter multiple solutions of the surface coverage exist at same applied potential. This mathematically explains the S-shaped negative differential resistance (NDR) feature in experimental Cyclic Voltammogram (CV) curves. Figure 1 shows three such experimental S-shaped curves for different concentration of suppressors. The NDR region obtained in the theoretical CV curve is sensitive to the kinetic parameters of the additives. It is possible to match the theoretical and the experimental CV curves by optimizing the kinetic parameters. Determination of the kinetic parameters by particle swarm optimization using experimental data for multiple additive concentration will be discussed in detail in this talk.

Electrocatalytic Properties of Pulse-Reverse Electrodeposited Nickel Phosphide for Hydrogen Evolution Reaction

Nickel phosphide (Ni-P) films as a catalytic cathode for the hydrogen evolution reaction (HER) of a water splitting were fabricated by a pulse-reverse electrodeposition technique. The electrochemical behaviors for the electrodeposition of Ni-P were investigated by the characterization of peaks in a cyclic voltammogram. The composition of the electrodeposited Ni-P alloys was controlled by adjusting duty cycles of the pulse-reverse electrodeposition. The HER electrocatalytic properties of the Ni-P electrodeposits with an amorphous phase as a function of phosphorous contents existing in Ni-P were electrochemically characterized by the analysis of overpotentials, Tafel slopes, and electrochemical impedance spectrometry. Additionally, the elemental Ni-embedded crystalline Ni3P was prepared by an annealing process with the amorphous Ni69P31 electrodeposit with high contents of phosphorus. The crystalline structure with Ni inclusions in the matrix of Ni3P was formed by the precipitation of excess Ni. The electrocatalytic properties of crystalline Ni3P with elemental Ni inclusions were also investigated by electrochemical characterization.

Some thermodynamic and kinetic properties of H2SO4–H3PO4–H2O–Fe(III) system

The values of the electrode potentials of the redox couple Fe(III) / Fe(II) and the half-wave potentials of the reactions Fe3+ + e– = Fe2+ и Fe2+ — e– = Fe3+ on the cyclic voltammogram of a platinum electrode in acid solutions containing Fe(III) salts have been measured to characterize the oxidizing ability of the H2SO4—H3PO4—H2O—Fe(III) system. The values of these experimentally obtained parameters are close. A decrease in the oxidizing ability of H2SO4 and H3PO4 mixtures containing Fe(III) with an increase in the molar fraction of H3PO4 in them occurs due to the formation of Fe(III) complexes with phosphate anions which are inferior to their hydrate and sulfate complexes in the oxidizing ability. The temperature coefficients of the electrode potential (dE / dt) of the redox couple Fe(III) / Fe(II) in the H2SO4—H2O, H2SO4—H3PO4—H2O and H3PO4–H2O systems were determined experimentally. The diffusion coefficients of Fe(III) in the studied solutions were calculated based on the Randles—Shevchik equation. The temperature dependence of the diffusion coefficients of Fe(III) cations is satisfactorily described by the Arrhenius equation. The parameters of this equation are calculated.

Cyclic Voltammogram Analysis of the Environmental Aspects of the Use of Ferrocenyl Carbinols

Ferrocene and its derivatives have ecologically effective antidetane properties. In this regard, ferrocene reacts with cyclic ketones and ferrosenylcarbinols are synthesized. It should be noted that ferrocene enters into electrophilic reactions and the process takes place in an acidic environment. In addition, the yield of the new product was small compared to the reactions of ferrocene with non-cyclic ketones. This is due to the spatial structures of molecules. The elemental analysis of obtained compounds was carried out; the structures were researched by cyclic voltammograms and Chronoamperometric.

Development of Electrochemical Aptasensor for Lung Cancer Diagnostics in Human Blood

We describe the preparation and characterization of an aptamer-based electrochemical sensor to lung cancer tumor markers in human blood. The highly reproducible aptamer sensing layer with a high density (up to 70% coverage) on the gold electrode was made. Electrochemical methods and confocal laser scanning microscopy were used to study the stability of the aptamer layer structure and binding ability. A new blocking agent, a thiolated oligonucleotide with an unrelated sequence, was applied to fill the aptamer layer’s defects. Electrochemical aptasensor signal processing was enhanced using deep learning and computer simulation of the experimental data array. It was found that the combinations (coupled and tripled) of cyclic voltammogram features allowed for distinguishing between the samples from lung cancer patients and healthy candidates with a mean accuracy of 0.73. The capacitive component from the non-Faradic electrochemical impedance spectroscopy data indicated the tumor marker’s presence in a sample. These findings allowed for the creation of highly informative aptasensors for early lung cancer diagnostics.

Electrochemical Study on MgO as an Additive in Molten Li2CO3-Na2CO3 for Molten Carbonate Fuel Cells

This study investigates the effect of MgO as an additive in molten Li2CO3-Na2CO3 electrolyte for molten carbonate fuel cells through electrochemical analyses. Addition of MgO (1~5 mol%) increased the electrochemical response in cyclic voltammogram of peroxide in molten Li2CO3-Na2CO3. The diffusion coefficient of peroxide in molten Li2CO3-Na2CO3 containing MgO was determined via the comparison between the peak currents of cyclic voltammograms from microwire electrode and macrowire electrode. The addition of MgO did not impact the diffusion coefficient, indicating that the increase in the electrochemical response with the addition of MgO might be attributed to the increase in the peroxide concentration. The change in peroxide concentration was also confirmed by electrochemical impedance analyses, which exhibited a decrease in the exchange current density. The increase in the concentration of peroxide with the addition of MgO might be associated with the high thermal decomposition constant of MgCO3, implying the high concentration of oxide ion in the molten Li2CO3-Na2CO3. This study suggests that MgO might be an effective additive for increasing the oxygen solubility in the molten Li2CO3-Na2CO3, and subsequently for enhancing the performance of molten carbonate fuel cells.

Cost effective dye sensitized solar cell based on novel Cu polypyrrole multiwall carbon nanotubes nanocomposites counter electrode

In order to replace Pt CE in dye sensitized solar cell (DSSC) with simple and low cost, copper polypyyrol functionalized multiwall carbon nanotubes (Cu-PPy-FWCNTS) nanocomposite CE was fabricated by two step electrodeposition method on the stainless-steel substrate. The surface morphology, electrical conductivity, electrochemical properties of Cu-PPy-FWCNTS nanocomposite CE electrodes were observed by using verity of techniques such as scanning electron microscopy, a four-probe method and electrochemical workstation. The Fourier transform infrared (FTIR) spectroscopy confirms the presence of FMWCNTS into PPy-FMWCNTS nanocomposite and XRD analysis verified the Cu nanostructures had come into being. The cyclic voltammogram and Tafel polarization measurement demonstrated that solution processed Cu-PPy-FWCNTS nanocomposites CE had smaller charge transfer resistance Rct (4.31 Ω cm2) and higher electrocatalytic performance for I3−/I− redox solution. Finally, the photovoltaic efficiency of DSSC assembled with Cu-PPy-FWCNTS nanocomposite CE and Platinized CE were compared. The results revealed that the photovoltaic efficiency of DSSC with Cu-PPy-FWCNTS nanocomposites CE reached (7.1%), which is superior to Platinized CE (6.4%). The higher photovoltaic efficiency of the Cu-PPy-FMWCNTS film is due to copper nanostructures that lead to higher cathodic current density (2.35 mA/cm2). The simple fabrication method, excellent electrocatalytic and photovoltaic properties permit the Cu-PPy-FWCNTS nanocomposites credible alternative CE to save the cost of DSSC.