Sharif Digital Repository

In this study, electrochemical oxygen reduction reaction (ORR) was studied on Cu, Pd, Rh, Pd-Cu and Rh-Cu alloys in alkaline solution. Pd-Cu and Rh-Cu alloys were prepared by electrochemical methods. On copper electrode it is found that direct oxygen reduction is accompanied by the electrochemical reductions of copper oxides. Also, mechanism and kinetics of reaction change as the amount of copper oxides increase on the surface. For electrodeposited alloys, it is indicated that the reactivity of Pd-Cu and Rh-Cu alloys toward oxygen reduction is higher than pure Pd and pure Rh. The maximum reactivity among Pd-Cu alloys is related to the sample with 24.5% copper content while the maximum... 

Electrocatalytic oxidation of L-ascorbic acid (L-AA) on silver electrode in alkaline solutions was studied employing cyclic voltammetry, chronoamperometry and impedance spectroscopy techniques. In comparison to Pt, the onset potential for L-AA electro-oxidation process on Ag, in a solution containg 0.02 M L-AA and 0.5 M NaOH, was 0.1 V more negative. Also, L-AA oxidation current increased more than 900% at -0.26 V/SCE. According to voltammety and impedance spectropy findings, although hydroxide anion presence was vital for L-AA oxidation to occur, at potentials more positive than -0.2 V/SCE, hydroxide ion tends to inhibit the oxidation process. Studies on the L-AA oxidation process on Ag in... 

This work investigates adsorption and possible dissociation of a number of small molecules on small clusters and carbonic surface. Theoretical study of carbon monoxide adsorption on SixGe4_x(x=0–4) nano-clusters has been carried out using MPW1B95 density functional. The geometry, adsorption energy, charge distribution, and vibrational frequency of CO adsorption on all possible structures were investigated. The maximum vibrational frequency changes occur in the bridge structures while the most stable structures occur when CO adsorbs on one silicon atom in a flat surface. Adsorption energies of CO on one Si atom are by far more negative than the corresponding value for on Ge atom. Theoretical... 

The purpose of this project is the prediction of the activation barriers and enthalpy for elementary steps in the process of Fischer-Tropsch over the surfaces of Fe, Cu and Fe/Cu alloys catalyst by using of UBI-QEP method aiming at finding prediction of the activity and selectivity on the basis of energy criteria.
UBI-QEP methods is based on conservation of bond index of adsorbed molecules and follow the quadratic exponential potential for energy, calculate the enthalpy and activation barriers of reaction pathways in a heterogeneous catalytic process and select the most desirable path to take.
The elementary steps such as dissociation of CO, hydrogenation of carbidic carbon, C-C... 

The aim of this project is to investigate the mechanisms of absorption and reactions of H2, O2, HCO2H on the single crystal surfaces of transition metals alloys such as Ni-Cu and Ni-Fe and …as well as the ability to control the properties of the mentioned alloys with change in constitutions percentage. In order to achieve the objectives, Unity Bond Index-Quadratic Exponential Potential, UBI-QEP method have been employed. Using this method, the thermodynamic parameters (heat of adsorption and reaction enthalpy changes) and kinetic parameters (activation energy of the reaction) can be calculated, and using these results, intermediate, and as a result, the mechanism of heterogeneous catalytic... 

We tried to collect electrode kinetics, transport separator and structural data about the existing RFB, mainly all V-based and try to simulate the behavior of these batteries under various load and different fluid injection conditions. The behavior of the potential-current, power-current and potential-time at different levels of concentration, flow, pH, .... were studied . The results between the two modes with the membrane and without the membrane in the batch battery were compared. Batch battery with membrane shows improved performance. Increasing the concentration of vanadium and reduceing the current at the flow battery decreases the gap between the charge and discharge state  

In Li batteries, lithium ions are exchanged between two electrodes, along with the accompaning electron transfer to maintain riability good ionic conductivities and electrolytes stability are achived through additives to the electrolyte. Such matrial should possess good anions acceptability. This work investigates the potential of aza-ethers in this regard. The softness criteris is basically employed. DFT calculation for selected molecules of different size, substituents and interacting atoms are used to correlate softness, electrophilicity, Fukui no, etc to the usefulness of the corresponding matrials  

A study of the electro-oxidation and surface reactions of C1 compounds on Ni and Cu electrodes, Ni(111) and Cu (111) has been performed by methods of cyclic voltammetry, BOC-MP and DFT. The diffusion coefficients and activation energies of the electro-oxidation of methanol and formaldehyde in alkaline solution on Ni electrode have been derived. Values around 2.27×10-6 cm2s-1, 1.98×10-5cm2s-1, 12.15 Kcal mol-1 and 11.65 Kcal mol-1 have been obtained respectively. In theoretical study , the elimination of hydrogen from CH3 and CH2 groups has been proposed as a mechanism in surface reactions of methanol and formaldehyde on Ni(111) ... 

In this work, Unity Bond Index-Quadratic Exponential Potential (UBI-QEP) method was applied to investigate the decomposition routs of -halo alcohols on Ni(111) and Cu(111) crystallographic planes and Ni2Cu1(111) and Ni1Cu2(111) alloys. UBI-QEP calculates energetics, H and E, along reactions routes using heats of atomic adsorption as empirical inputs and in this way avoids needs to be very specific about every system. The results of analysis of -halo-propanols on Ni and Cu surfaces are in good agreement with experimental findings; namely in the formation of carbon-monoxide, ethylene, water and hydrogen over Ni and propene and water over Cu. Predicted activity of -halo-propanols,... 

Impedance measurement is one of the most efficient electrochemical methods to investigate the mechanism and kinetics of electrode reactions. This method can detect the steps of successive or parallel electron and mass transfer chemical reactions based on measuring the response time constant. The method of showing results, commonly known as Nyquist diagram,which is based on drawing real and imaginary components of the impedance, with respect to each other in different measurement frequencies, is very useful for determining the mechanism of electrode reactions and the kinetic measurements. The main objective of this thesis is totheoretically determine the impedance response of six... 

In this thesis, the improving effects of deposited metal oxides onto or next to each other and the advantages of every metal oxide were considered. In the next step, the substrate improvement was studied and the porous metal oxides with ideal supercapacitive properties with porosity increase of substrate were obtained.CoFeO2 supercapacitor was prepared by chronoamperometric ethod.CoFeO2waselectrodeposited at room temperature and presents wide potential window and good capacitive properties in comparison with other metal oxides.Layers of cobalt and manganese oxides were co-deposited or deposited on top of each other or next to each other by chronometric method onto stainless steel substrate.... 

In this thesis, the improving effects of TiO2 nanotubes (TiO2NTs) fabricated by anodizing of titanium as suitable substrate for deposition active materiales in supercapacitors were considered. PANI/Pd/TiO2NTs electrodes with highly porous structures and good capacitive characteristics were prepared by electrodeposition of polyaniline on palladium nanoparticles loaded TiO2 nanotubes. The results illustrated that the specific capacitance of these electrodes was around 1060 Fg−1 in 1.0 M H2SO4 electrolyte as measured at a constant current of 2.0 Ag−1, whereas it was 210 Fg−1 for the PANI/TiO2NTs electrode. NiO-ZnO/TiO2NTs electrodes were synthesized by the electrodeposition of... 

Estimation of physical parameters for solutions and mixed liqids are used widely in industrial applications. However, we can do these measurements with conventional laboratory analysis, but we always want to find an easy and quick method that use on-line measurements. In this study electrical properties of different water liquids and mixture samples in frequency stepwise range of 100-100000 Hz are measured by using a short cylindrical capacitive sensor and a measuring module (LCR-703).Operation of the capacitance measurement module for such probes is based on the auto-balancing bridge method.The effects of frequency and volume fraction on the electrical parameters and permittivity of mixed... 

The electrical conductivity of the solution has been one of the important physical quantities in many application. In this respect many probes and devices such as conductive sensors have been devised. In this study electrical properties of different water samples at frequency step range of 100-100000 Hz are measured by using the long cylindrical capacitive sensor and a measuring module (LCR-703). Operation of the capacitance measurement module for such probes is based on the auto balancing bridge method. Comparison of the measured capacitances and measured resistances for different water samples shows a decrease by increasing the measurement frequency. In another study the dielectric...