Sharif Digital Repository

Agglomerates of tungsten trioxide in the range of 90 nm to 1 μm are prepared by the acid precipitation method and characterized by XRD as well as scanning electron microscopy. The product when coated with platinum showed pseudocapacitance when in contact with acidic electrolyte in the potential range of 0. 1 to -0. 25 V/SCE. Capacitance in the range of 0. 014 to 0. 039 F cm-2 exhibiting moderate potential dependencies measured through both chronopotentiometry and impedance spectroscopy is presumed to be due to the insertion/de-insertion of protons into the lattice of tungsten trioxide. Equivalent circuit consisting of parallel simulators of mass transfer and capacitor charging... 

Density functional theory is used in a spin-polarized plane wave pseudopotential implementation to investigate molecular oxygen adsorption and dissociation on graphite and nickel-doped graphite surfaces. Molecular oxygen physisorbs on graphite surface retaining its magnetic property. The calculated adsorption energy is consistent with the experimental value of 0.1eV. It is found that substituting a carbon atom of the graphite surface by a single doping nickel atom (2.8% content) makes the surface active for oxygen chemisorption. It is found that the molecular oxygen never adsorbs on doping nickel atom while it adsorbs and dissociates spontaneously into atomic oxygens on the carbon atoms... 

The adsorption and dissociation of H2O2 on small PdxM3-x (M=Pt, Cu; x = 1-3) clusters is investigated using the B3PW91 hybrid density functional method. Natural bond orbitals are analysed to obtain partial charges on atoms, dipole moments, bond orders, and hybrid orbitals of the PdxM3-x-H2O2 systems. The calculated adsorption energies are in the range of -0.32 to -2.12 eV. Generally, H2O2 adsorbs on top positions through one of its oxygen atoms and only in a few cases reacts with the cluster through both oxygen and hydrogen sides. In the latter case the cluster sites which are negatively charged interact with the hydrogen atoms. Interestingly, on the triplet Pd2Pt cluster, H2O2 dissociates... 

Theoretical study of nitrogen monoxide adsorption on small Six (x = 3-5) clusters has been carried out using the advanced hybrid meta-density functional method of Truhlar (MPW1B95). MG3 semi-diffuse basis sets were employed to improve the results. The geometry, adsorption energy, natural bond orbital charge, natural population analysis (NPA)-derived spin density and vibrational frequency of NO adsorption on all optimized nanoclusters were investigated. Also using the NPA, we have investigated the change of bond orders through adsorption. It has been found that NO is capable of making n-centre bonds (n = 1-4) from the nitrogen side but bonds to one site from the oxygen end. In the later case... 

Our previously reported mathematical model for a mixed oxide nanoparticulate-based supercapacitor containing RuO2·xH2O and MO2·yH2O (M being another suitable transition metal) was analyzed. Both double-layer and faradaic processes responsible for charge/discharge were considered. The effects of the intrinsic factors, unit cell length, state of charge, and the exchange current densities of the electrochemical processes of the constituents on the performance of the model supercapacitor were clarified. Compensation effects where each constituent compensates the shortcomings of the other at specific conditions of discharge are analyzed in the light of the model  

Impedance characteristics of the negative electrode of lead-acid battery were derived on the basis of fundamental interfacial processes occurring at the electrode. The solution of the governing equations was presented in terms of a simple equivalent circuit consisting of resistive and capacitive loops in which charge transfer and sulfate layer formation and also mass transfer (Warburg) elements are considered. The kinetic parameters were deduced by fitting the theoretically derived impedance to the experimental data. Impedance at various States of Charge (SoC) was also examined  

Electrochemical oxidation of l-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at -500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10-5 cm2 s-1. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm-2 and 4 mF cm-2 as well as the adsorption and decomposition resistances (rates). © 2009 Elsevier B.V. All... 

Theoretical study of carbon monoxide adsorption on SixGe4 - x(x = 0-4) nano-clusters has been carried out using advanced hybrid meta density functional method of Truhlar (MPW1B95). MG3 semi-diffuse (MG3S) and correlation consistent valence basis sets with relativistic core potential were employed to improve the results. The agreement of the calculated ionization and dissociation energies with experimental values validates the reported structures of nano-clusters and justifies the use of hybrid meta density functional method. The geometry, adsorption energy, charge distribution, and vibrational frequency of CO adsorption on all possible structures were investigated. The maximum vibrational... 

Adsorption and dissociation of NO on RhxCu4-x(x = 0–4) nano clusters were investigated using density functional theory. Adsorption energy, total charge on NO, NO bond length, and NO vibrational frequency for various modes of NO adsorption were analyzed. Adsorption from the nitrogen end of NO on the Rh atom(s) of the clusters are more favored and adsorption energies are in the −1.02 eV to −2.59 eV range. NO binds stronger to Rh-Cu mixed clusters compared to pure Cu4 cluster, so N[sbnd]O bond is significantly weakened upon adsorption on the former. NO binding to more atoms of the clusters results in a corresponding decrease of the N[sbnd]O vibrational frequency. Dissociation of NO was also... 

A mathematical model was developed to describe the performance of nanoparticulate mixed oxide pseudocapacitors based on RuO 2-MO 2 (M being another suitable transition metal) under galvanostatic charge/discharge regime. Both double layer and faradaic processes were taken into account. The effects of the active material's particle size and composition were examined. Furthermore, the influence of discharge current on the extents of double layer and faradaic contributions was analyzed. The model analysis showed that the energy density declined upon increasing the volume fraction of larger particles. © 2008 Springer-Verlag  

Using the gradient-corrected hybrid density functional method of Predew, Burke, and Ernzerhof (PBEPBE) and the new hybrid meta-density functional method of Truhlar (MPW1B95), the geometry, adsorption energy, vibrational frequency, and charge distribution of carbon monoxide adsorption on a Si4 nano-cluster has been studied. Taking into account spin multicipility in the calculations, a new stable structure of CO absorbed on the Si4 cluster has been found, in addition to the previously reported structures. Exhaustive vibrational frequency analysis of optimized structures shows that some of the formerly reported structures have imaginary vibrational frequencies and are not proper stable... 

The factors influencing the electrochemical behaviour of a supercapacitor have been partly examined in this work. The effects of so-called intrinsic parameters, i.e. exchange current density, unit cell length and double layer (DL) capacitance; as well as the so-called application parameters, i.e. cell current, on the cell potential discharge time have been considered. The contributions of each type of capacitors, DL capacitor and faradaic supercapacitor under various states of operation and material have been analyzed, and the competing (compensating) effects of the two types of capacitors as regards to the discharge and power characteristics manifested by current-potential and energy-power... 

Artificial neural network was used to calculate the performance of a model supercapacitor as signified by the power density, energy density and utilization to the synthetic, intrinsic and operating characteristics. A four-layer neural net having two hidden layers having 6 and 15 nodes was found to be well capable of simulating the capacitor performance with the convergence achieved often a relatively small number of epochs. As for the input parameters, crystal size, surface lattice length, exchange current density of the capacitor active material and the cell current employed while utilization, energy density and power density were the outputs. © 2006 Elsevier B.V. All rights reserved  

A neural network based on the feed forward back propagation error has been developed for the design and simulation of the catalytic properties of a multi-component system based on Cu-M-Al2O3 (M=Zn,Cr,Zr) for the steam reforming of methanol. Due to the limited size of the data set, cross validation method has to be used to enhance and also evaluate the prediction ability of the network. The best structural organization has been found to include 4,3,6,3 nodes in the input, two hidden layers and the output layer respectively  

The rate constants of the oxidation of CO on a number of pure and La 2O3 doped NiO/Al2O3 solid catalysts were correlated with the mole percent of dopant, calcinations temperature, surface area, pore volume and pore mouth diameter by an artificial neural network simulator. The cross validation method had to be used due to the scarcity of the data. A three-layer network with 3 nodes in the hidden layer was found to simulate the system well. © Akadémiai Kiadó, Budapest. All rights reserved  

The method of unity bond index-quadratic exponential potential (UBI-QEP) is employed to derive the energetic parameters associated with the steps of the pathway which we propose for the catalytic decomposition of azomethane on the Pd(111) surface. According to the energy calculations, azomethane adsorbs molecularly in trans-configuration and then decomposes to CH3N with no activation energy. The reaction continues by tilting and dehydrogenation to the products (H2 and HCN). The calculated activation energies at various surface coverages perfectly account for the variation of relative yields of H2 and HCN with changing of the coverage of azomethane. According to the calculations, desorption... 

Electrodeposition/dissolution of cadmium onto a film of mercury shows some deviations from the natural liquidity of mercury caused by the reduction of Cd onto it. Percolation and fractal analyzes were done on the surface and the bulk of the mercury film during diffusion of Cd species (atoms). These show that the fractal dimensions of the Cd-inserted mercury film are about 2.11 and 2.54 near the surface of the mercury film and at deeper points inside the film, respectively. The insertion process has a negligible effect on the surface morphology of the mercury film and there is a phase transition in the bulk, as well as a geometrical transition during the Cd-insertion (de-insertion) process.... 

The energetics of the adsorption and decomposition of ammonia on Nb(100) surface was investigated by the method of unity bond index-quadratic exponential potential (UBI-QEP). The experimental as well as theoretically derived atomic heats of adsorption were used as the input data and the results were compared with the findings of local density functional theory (LDFT) and non-local density functional theory (NLDFT). The method was capable of correctly predicting the fragmentation of ammonia on 4-fold hollow sites on the surface of Nb(100) and magnitudes of the heats of adsorption and activation energies were more realistic  

The decomposition of methyl iodide on Cu(110) surface gives rise to the production of methane, ethane, and ethene over a wide range of its surface coverage. In this work a reaction mechanism based on the adsorption and subsequent surface dissociation(s) of methyl iodide followed by the recombination and desorption of the surface entities are proposed on the basis of the energetic criteria provided by the unity bond index-quadratic exponential potential method. To further amplify the arguments using the calculated activation energies of the surface reactions, desorptions, etc., the Arrhenius factor is obtained by simulation of the temperature-programmed desorption patterns fitted to the... 

The method of unity bond index-quadratic exponential potential (UBI-QEP) and the computer simulation of the temperature programmed desorption (TPD) patterns are employed to derive the kinetic and thermodynamic parameters associated with the steps of the pathway we propose for the catalytic decomposition of methyl iodide on the Cu(111) surface. Assuming a highly reactive `hot methyl' surface intermediate and on the basis of our calculations it is concluded that the desorption of a part of this species is responsible for the reported methyl radical TPD peak at 140 K, while a part of this surface species is trapped in the three-fold sites of the Cu(111) surface and desorbs to form the reported...