Sharif Digital Repository

We have studied systematically photocatalytic properties of the vertically aligned ZnO@CdS core-shell nanorods where the features were grown through a multistep procedure including sol-gel for the formation of ZnO seed layer, hydrothermal process to grow ZnO nanorods, and successive ion layer adsorption and reaction (SILAR) process to deposit CdS nanoshells onto the ZnO nanorods. Formation of the ZnO seed layer and vertically aligned ZnO nanorods (d ∼ 40 nm) with a hexagonal cross-section was confirmed by AFM and SEM imaging. Successful capping of ZnO nanorods with homogeneous CdS nanocrystallites (∼5 nm) was ascertained by HRTEM diffraction and imaging. Optical properties of the samples... 

A novel efficient and cost-effective heterogeneous catalyst for the production of biodiesel from transesterification of sunflower oil was prepared through the impregnation of K2CO3 upon the Talc material. The physicochemical features of the catalyst were studied through several characterization analyses. The effect of the K2CO3 loading was investigated by comparing the catalytic activity of various prepared catalysts. Moreover, the effect of the calcination temperature upon the catalytic activity was examined. To maximize the yield of the produced biodiesel fuel, reaction variables such as the reaction time and temperature, catalyst concentration, and methanol: oil molar ratio were... 

A developed route to form TiO2 self cleaning coatings on polycarbonate substrates is reported. TiO2 coatings on plastics may find widespread application in auto and construction industries if possess desired photocatalytic and mechanical properties. A chemical surface treatment method was used to create hydrophilic groups on the surface. X-ray photoelectron spectroscopy showed the treatment led to the oxidation of surface groups. TiO2 deposition was based on wet coating using an anatase sol of TiO2 nanoparticles of 30 nm size. The sol was synthesized using a sol-gel route. A pre-coat of peroxotitanium complex was employed to improve adhesion and inhibit the substrate degradation. The coating... 

In the present study, a procedure was developed to determine the optimum reaction rate constants in generalized Arrhenius form and optimized through the Nelder-Mead method. For this purpose, a comprehensive mathematical model of a fixed bed reactor for dehydrogenation of heavy paraffins over Pt-Sn/Al 2O 3 catalyst was developed. Utilizing appropriate kinetic rate expressions for the main dehydrogenation reaction as well as side reactions and catalyst deactivation, a detailed model for the radial flow reactor was obtained. The reactor model composed of a set of partial differential equations (PDE), ordinary differential equations (ODE) as well as algebraic equations all of which were solved... 

V2O5/SiO2 catalyst utilized to oxidize the SO2 to SO3 species in the presence of oxygen mainly for producing sulfuric acid. For this catalyst, the active phase was a mixture of vanadium pentoxide and basic sulfate/pyrosulfate material. This active phase at the reaction temperature behaved as a liquid filling up the pores of the silica support. On the other hand, amounts of the SO3 and V5+ species in the catalyst necessarily varied with the concentration of the feed material and temperature rendering complexity to the kinetics of the SO2 oxidation reaction. In the current research, the catalyst preparation with different amounts of such materials was undertaken. Purified Diatomaceous earth of... 

By combination of 1-ethyl-3-methyl immidazolium ethyl sulfate as a typical room temperature ionic liquid (IL) and graphene oxide (GO) nanosheets, a nanocomposite was introduced for improving the direct electrochemistry and electrocatalytic activity of glucose oxidase (GOx). The enzyme on the IL-GO-modified glassy carbon electrode exhibited a quasireversible cyclic voltammogram corresponding to the flavine adenine dinucleotide/FADH2 redox prosthetic group of GOx. At the scan rate of 100 mV s-1, the enzyme showed a peak-to-peak potential separation of 82 mV and the formal potential of -463 mV (vs Ag/AgCl in 0.1 M phosphate buffer solution, pH 7.0). The kinetic parameters of the charge transfer... 

Horseradish peroxidase (HRP) was successfully immobilized on amine functionalized TiO 2-coated multiwalled carbon nanotubes (NH 2-TiO 2-CNTs) by a convenient and efficient method. Electrochemical impedance spectroscopy, cyclic voltammetry and amperometry were applied to characterize the HRP/NH 2-TiO 2-CNT nano-composite. These techniques showed that the NH 2-TiO 2-CNTs greatly enhance the electron transfer between HRP and the modified electrode. Owing to the redox reaction of the electroactive centre of HRP, the HRP/NH 2-TiO 2-CNTs modified electrode exhibited a pair of quasi-reversible peaks with a peak-to-peak separation (ΔE p) of 70.6mV and a formal potential (E 0′) of -367.65mV (versus... 

A nano-composite material consisting of amine functionalized TiO 2-coated carbon nanotubes was prepared and used for glucose oxidase (GOx) absorption. The GOx bearing nanomaterial was fixed on a glassy carbon electrode to construct a novel biosensor for glucose determination. The direct electrochemistry of immobilized GOx and its electron transfer parameters at the modified glassy carbon electrode were reported. The apparent heterogeneous electron transfer rate constant (ks) of GOx was estimated to be 3.5 s-1, which is higher than those reported previously. Amperometric detection of glucose resulted in a rapid (3 s) and stable response in the linear concentration range from 1.8 to 266 μM.... 

In this article, the synthesis, characterization, and cyclic voltammetry (CV) measurements are reported for ferrocene-terminated oligophenyleneimine (OPI_Fc) and ferrocene-terminated conjugation-broken oligophenyleneimine (CB-OPI_Fc) self-assembled monolayers (SAMs) in two different electrolytes, namely, 1-ethyl-3-methylimidazolium-bis (trifluoromethyl-sulfonyl) imide (EMITFSI) ionic liquid and tetrabutylammonium hexafluorophosphate (Bu4NPF6) in acetonitrile (0.1 M solution). The SAMs were synthesized on Au surfaces by the sequential imine condensation reactions. CV was used to investigate the kinetics of electron transfer (ET) to the ferrocene, and it was observed that the standard ET rate... 

A gas-phase heterogeneous kinetics is described over perovskite with formula La0.6Sr0.4Co0.8Fe0.2O3-δ (LSCF) for the oxidative coupling of methane under differential conversion conditions in a microcatalytic fixed-bed reactor. The ethane (C2H6) and carbon oxides (COX) formation and methane conversion rates were obtained as a function of methane and oxygen partial pressure under experimental conditions of: 0.20 < PC H4 < 0.82 atm, 0.04 < PO2 < 0.15 atm, and 1073 < T < 1173 K. The different kinetic models were examined and two Eley-Rideal mechanisms (a and b) were successfully performed to fit the experimental data into the theoretical relations from which two mechanisms having a first step of... 

The hydrogen abstraction reaction of the OH radical with CH 3CHF2 (HFC152-a) has been studied theoretically over a wide temperature range, 200-3000 K. Two different reactive sites of the molecule, CH3 and CHF2 groups have been investigated precisely, and results confirm that CHF2 position of the molecule is a highly reactive site. In this study, three recently developed hybrid density functional theories, namely, MPWB1K, MPW1B95, and MPW1K, are used. The MPWB1K/6-31+G(d,p) method gives the best result for kinetic calculations, including barrier heights, reaction path information and geometry of transition state structures and other stationary points. To refine the barrier height of each... 

The 1H-13C coupling constants of methyl α- and β-pyranosides of d-glucose and d-galactose have been measured by one-dimensional and two-dimensional 1H-13C heteronuclear zero and double quantum, phase sensitive J-HMBC spectra to determine a complete set of coupling constants (1JCH, 2JCH, 3JCH, 2JHH, and 3JHH) within the exocyclic hydroxymethyl group (CH2OH) for each compound. In parallel with these experimental studies, structure, energy, and potential energy surfaces of the hydroxymethyl group for these compounds were determined employing quantum mechanical calculations at the B3LYP level using the 6-311++G** basis set. Values of the vicinal coupling constants involving 1H and 13C in the... 

The simultaneous oxidation performance of benzene, toluene, ethylbenzene, and xylene (BTEX) by nanoscale calcium peroxide particles (nCaO2) activated with ferric ions (Fe(III)) and the mechanism of the enhancement of BTEX degradation by L-cysteine (L-cys) were investigated. The batch experimental results showed that the nCaO2/Fe(III)/L-cys process was effective in the destruction of BTEX in both ultrapure water and actual groundwater. A proper amount of L-cys could enhance BTEX degradation due to the promotion of Fe(II)/Fe(III) redox cycles by the participation of L-cys, but an excessive presence of L-cys would cause inhibition. Adding 1.0 mM L-cys to the nCaO2/Fe(III) system, the... 

Corrosion of mild steel in aqueous solutions containing hydrogen sulphide was modelled under the condition that an iron sulphide film was formed on the steel surface. In the present model, the iron sulphide forms on the steel surface as a result of a solid state reaction between iron and hydrogen sulphide which has several steps. First a very thin film of iron sulphide nucleates on the steel surface. Then, due to further growth of the initial thin layer, a more porous layer of iron sulphide forms on the initial film. In the present model, it is assumed that mass transfer through the thin iron sulphide layer (i.e. adjacent to the steel substrate) controls the corrosion rate of steel in H 2S... 

A model for prediction of corrosion of mild steel in aqueous solutions containing carbon dioxide is proposed. In this model, formation of protective corrosion product is not yet considered, species concentration at the surface was calculated by using molecular diffusion phenomena and the diffusion equations were solved using the finite difference method. Calculated electrochemical currents at the steel surface may be used to determine the corrosion rate. The model was verified experimentally under atmospheric pressure and the effect of parameters, such as liquid velocity and pH, was investigated. The model can predict the electrochemical reaction rates when they were controlled by diffusion... 

Developing an efficient visible-light-driven photocatalyst is believed to be a practical solution for clean energy and environmental remediation. The present study aimed to broaden current knowledge of the graphitic carbon nitride (g-C3N4)-based plasmonic photocatalysts by decorating polydopamine-grafted g-C3N4 (PDA/g-C3N4) with silver nanoparticles (AgNPs). The nanocomposite was prepared using a facile synthesis method, while XPS and microscopy measurements confirmed the homogenous dispersion of AgNPs on PDA/g-C3N4. AgNPs successfully reduced the recombination rate of photoinduced electron-hole pairs. The calculated bandgap energy was decreased from 2.7 eV for pure g-C3N4 to 2.1 eV for... 

Mud filtration happens during an overbalanced drilling operation that causes mud invasion into pores and fractures. The productivity of a formation is significantly affected by the invasion of the mud into the near-wellbore area during the mud loss process. A considerable number of studies have evaluated mud filtration statically; however, a few studies have considered the dynamic behavior of a mud loss process during overbalanced drilling, which results in the inadequate prediction of the mud loss volume and inflicted damage to the formation. In this study, a near-wellbore simulation system (NeWSS) was designed to evaluate the dynamic mud loss behavior using dimensionless parameters and... 

Rate constants, k A, for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 2-propanol mixed with hexane, benzene, and 2-methylpropan-2-ol and 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]) with dimethyl sulfoxide at 25°C. The obtained rate constants of the reaction in pure solvents are in the following order: 2-methylpropan-2-ol > dimethyl sulfoxide > 2-propanol > hexane > benzene > [Emim][EtSO4]. Molecularmicroscopic solvent parameters corresponding to the selected binary mixtures were utilized to study the kinetics of a nucleophilic substitution reaction in order to investigate and compare the... 

Rate constants, k A, for the aromatic nucleophilic substitution reaction of 2-chloro-3,5-dinitropyridine with aniline were determined in different compositions of 2-propanol mixed with hexane, benzene, and 2-methylpropan-2-ol and 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]) with dimethyl sulfoxide at 25 C. The obtained rate constants of the reaction in pure solvents are in the following order: 2-methylpropan-2-ol > dimethyl sulfoxide > 2-propanol > hexane > benzene > [Emim][EtSO4]. Molecularmicroscopic solvent parameters corresponding to the selected binary mixtures were utilized to study the kinetics of a nucleophilic substitution reaction in order to investigate and compare the... 

The microscopic features of binary solvent systems formed by molecular solvents (methanol, ethanol, 2-methylpropan-2-ol, water, pyridine, acetonitrile, 1-propanol, 2-propanol, dimethylformamide) and the ionic liquid ([bmim]BF 4) as cosolvent were used to select mixed solvents with particular characteristics. Molecular-microscopic solvent parameters corresponding to these binary mixtures were utilised to study the kinetics of the nucleophilic substitution reaction between 2-chloro-3,5-dinitropyridine and aniline to investigate and compare the effects of the solvents on a model chemical reaction. For these mixtures, the solvation behaviour is dominated by both the dipolarity/ polarisability...