Improving Catalytic Activity in the Electrochemical Separation of CO2 Using Membrane Electrode Assemblies

The direct electrochemically driven separation of CO2 from a humidified N2, O2, and CO2 gas mixture was conducted using an asymmetric membrane electrode assembly (MEA). The MEA was fabricated using a screen-printed ionomer bound Pt cathode, an anion exchange membrane (AEM), and ionomer bound IrO2 anode. Electrocatalyst materials were physically and chemically characterized prior to inclusion within the electrode. Electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV) measurements using a rotating disk electrode (RDE) were used to quantify the catalytic activity and determine the effects of the catalyst-to-ionomer ratio. Catalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) surface analysis, and (dynamic light scattering) DLS to evaluate catalyst structure, active surface area, and determine the particle size and bulk particle size distribution (PSD). The electrocatalyst layer of the electrodes were fabricated by screen printing a uniformly dispersed mixture of catalyst, dissolved anionic ionomer, and a solvent system onto an electrode supporting gas diffusion layer (GDL). Pt IrO2 MEAs were fabricated and current-voltage relationships were determined using constant-current measurements over a range of applied current densities and flow rates. Baseline reaction kinetics for CO2 separation were established with a standard set of Pt-IrO2 MEAs.

Spray-Pyrolytic Tunable Structures of Mn Oxides-Based Composites for Electrocatalytic Activity Improvement in Oxygen Reduction

Hybrid nanomaterials based on manganese, cobalt, and lanthanum oxides of different morphology and phase compositions were prepared using a facile single-step ultrasonic spray pyrolysis (USP) process and tested as electrocatalysts for oxygen reduction reaction (ORR). The structural and morphological characterizations were completed by XRD and SEM-EDS. Electrochemical performance was characterized by cyclic voltammetry and linear sweep voltammetry in a rotating disk electrode assembly. All synthesized materials were found electrocatalytically active for ORR in alkaline media. Two different manganese oxide states were incorporated into a Co3O4 matrix, δ-MnO2 at 500 and 600 °C and manganese (II,III) oxide-Mn3O4 at 800 °C. The difference in crystalline structure revealed flower-like nanosheets for birnessite-MnO2 and well-defined spherical nanoparticles for material based on Mn3O4. Electrochemical responses indicate that the ORR mechanism follows a preceding step of MnO2 reduction to MnOOH. The calculated number of electrons exchanged for the hybrid materials demonstrate a four-electron oxygen reduction pathway and high electrocatalytic activity towards ORR. The comparison of molar catalytic activities points out the importance of the composition and that the synergy of Co and Mn is superior to Co3O4/La2O3 and pristine Mn oxide. The results reveal that synthesized hybrid materials are promising electrocatalysts for ORR.

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.

Surface Characterization of New Azulene-Based CMEs for Sensing

Films of 2-(azulen-1-yldiazenyl)-5-phenyl-1,3,4-thiadiazole (T) were successfully deposited on glassy carbon surfaces to prepare chemically modified electrodes (CMEs). Their surface characterization was analyzed by electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). This complexing monomer has been deposited through direct electropolymerization in conditions established during the electrochemical characterization of T performed by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and rotating disk electrode voltammetry (RDE). These methods put in evidence the high degree of asymmetry of oxidation and reduction curves, which is due to the irreversible processes occurring at opposite potentials. The film formation was confirmed by ferrocene redox assay probe. The properties of the electrodes modified with T (T-CMEs) were investigated for sensing heavy metal (HM) ions in water solutions, with promising results for Pb(II) among Cd(II), Cu(II), and Hg(II) ions.

Selection of rational electrochemical methods for controlling the efficiency of machining of corrosion-resistant steel

The article discusses methods of controlling the processes of mechanical processing based on electrochemical effects. The corresponding anodic polarization curves of 1X18H9T steel obtained in electrolyte solutions without and with stirring are presented. The article discusses methods of machining processes control based on electrochemical effects. Lubricating and cooling technological media (LCTM) used in machining are in most cases electrolytes, therefore, electrochemical processes and phenomena actively occur during contact dynamic machining. It is possible to control the processes of machining by acting on the system elements of the tool - LCTM- part, in particular by activating the LCTM and reducing the strength characteristics of the processed steel in the cutting zone. A reserve for increasing the efficiency of mechanical processing can be the composition selection of the applied LCTM, combined with the simultaneous electrochemical polarization of the treated surface of friction pair parts. It was found that when cutting, the efficiency of machining and the chip shapes are changed, which is explained by the influence of the current density on the strength of the processed steel. In the conditions of machining, complex dynamic processes occur due to the rotation of the work piece and/or tool, so it is necessary to take into account the hydrodynamic phenomena and processes that arise in this case. Electrode potentials are considered to be the most important characteristic of the metal cutting process. The potential of the system can regulate such processes and indicators as wear and surface micro hardness. Anodic polarization curves of the steel 1X18H9T obtained in various electrolyte solutions without stirring and with stirring on a rotating disk electrode are given. The study allowed determining the factors affecting the processes occurring in the cutting zone and to identify rational current densities due to simulating the conditions of real technological processes of the combined steel processing. The increase in the processing intensity of the steel 1X18H9T with the cutting zone polarization is associated with the action of factors activating the selective anodic dissolution of the processed alloy.

Carbon-Supported Pt-SnO2 Catalysts for Oxygen Reduction Reaction over a Wide Temperature Range: Rotating Disk Electrode Study

Pt/C and Pt/x-SnO2/C catalysts (where x is mass content of SnO2) were synthesized using a polyol method. Their kinetic properties towards oxygen reduction reaction were studied by a rotating disk electrode (RDE) technique in a temperature range from 1 to 50 °C. The SnO2 content of catalyst samples was 5 and 10 wt.%. A quick evaluation of the catalyst activity, electrochemical behavior and average number of transferred electrons were performed using the RDE technique. It has been shown that the use of x-SnO2 (through modification of the carbon support) in a binary system together with Pt does not reduce the catalyst activity in the temperature range of 1–30 °C. The temperature rising up to 50 °C resulted in composite catalyst activity reduction at about 30%.

A new spin on electrochemistry in the undergraduate lab

The growing interest in electrochemistry over recent years has sparked an increase in the popularity of various electrochemical techniques, including more advanced methods, that have previously been overlooked in academia and industry. This makes comprehensive hands-on experience in electrochemistry a highly demanded addition to chemistry graduates. However, many students do not receive sufficient training in the theory and experimental design to confidently use and apply various electrochemical techniques throughout their undergraduate, and sometimes even in graduate studies. Here we summarize the theory and practical applications for both rotating disk electrode (RDE) and rotating ring disk electrode (RRDE) techniques. The different modes of operation of rotating ring disk voltammetry, methodologies of data analysis and interpretation as well as the scope of the information that can be extracted from the RDE/RRDE are discussed. Proposed modifications of the laboratory curriculum will allow students to examine and learn valuable information about the reactions on the surface of the electrode/liquid interface. This information will allow chemists to confidently use RDE and RRDE techniques for a wide range of research and development targets. Furthermore, incorporating these techniques into existing chemistry laboratories will help chemistry educators to enrich the undergraduate chemistry curriculum and improve students’ learning outcomes.

Theoretical and Experimental Study of Current from Non-Disintegrable Suspended Particles at a Rotating Disk Electrode

Understanding the current response at an electrode from suspended solid particles in an electrolyte is crucial for developing materials to be used in semi-solid electrodes for energy storage applications. Here, an analytical model is proposed to predict and understand the current response from non-disintegrable solid particles at a rotating disk electrode. The current is shown to be limited by a combination of ion diffusion within the solid particle and the mean residence time of the particle at the rotating disk electrode. This results in a relationship between current and angular frequency of I∝ω^(3/4), instead of the classical I∝ω^(1/2) predicted by Levich theory. Specifically, the current response of Li4Ti5O12 (LTO) microparticles suspended in a non-aqueous electrolyte of lithium hexafluorophosphate (LiPF6) in ethylene carbonate: diethyl carbonate (EC:DEC) was determined experimentally and compared favorably with predictions from the proposed analytical model using fitting parameters consistent with the experimental conditions.