Sharif Digital Repository

Ab initio, DFT, Monte Carlo statistical mechanics and atom in molecule methods have been applied to investigate the hydrogen bonding effect of protic solvents, apart from the bulk properties, on the reaction of cyclopentadiene and vinyl acetate. The results show that methanol accelerates the rate of the reaction more than water. DFT calculations demonstrate that the interaction of the carbonyl group oxygen atom with solvent molecules in transition state is stronger and more effective than the ether-type oxygen atom. Also, when the solvent molecule is near the oxygen of the carbonyl group the rate of reaction is larger than when it is near the ether-type oxygen. In addition, methanol... 

Ag2O particles were loaded on the surface of ZnCr-LDH via an anion-exchange precipitation approach by using privilege of the memory trace feature of the LDH-type materials. The structural properties of the resulted photocatalyst were explored by different spectroscopic and microscopic methods. The photocatalytic studies on acid black degradation ascertained that the prepared Ag2O/ZnCr-LDH nanocomposite represented an observably increased degradation performance of organic pollutants compared with pure Ag2O and ZnCr-LDH. This improved photocatalytic performance can be ascribed to the enhanced surface area, good order distributing of particles and effective charge carrier transfer and... 

Metal Organic Frameworks (MOFs) have received enormous attention in catalysis field due to their special structures and various promising applications. One of the intriguing applications of MOFs is utilization of them as precursors for synthesis of metal oxide nanomaterials. Base on this strategy, in this work, we have applied Cu-MOF to prepare a series of noble metal nanoparticles (Ag and Au) decorated CuO (M/CuO) as efficient catalyst. As-prepared nanocomposites were characterized by various analytical techniques and their catalytic performances appraised by using of the catalytic reduction of p-nitrophenol to p-aminophenol as a reliable model reaction. Experimental results suggest that... 

Ab initio quantum mechanics and ONIOM calculations were used to study solvent and substituent effects on the reactions of 1,4-benzoquinone with cyclopentadiene and cyclohexadiene derivatives in tetrahydrofuran and greater water solvents. These calculations revealed (i) that increasing the number of electron donating methyl group substituents and (ii) the proximity of substituents to the reacting carbons (carbon atoms which contribute to the forming C-C bonds) on the diene, promote charge transfer from the diene to the dienophile in the transition state. © 2008 Science Reviews 2000 Ltd. These effects increase the negative charge on the oxygen atoms, destabilize the transition state in the... 

The kinetics and mechanism of the reactions of hydroxylamine and aminoxide anion with methyl iodide were studied with ab initio calculations, Monte-Carlo and QM/MM simulations in gas and aqueous phases. Geometrical parameters and charge calculations show that these reactions proceed through the SN2 (bimolecular nucleophilic displacement) mechanism only. The solvent effects on these reactions were studied by inserting water molecules in reaction media, Onsager model, Monte-Carlo and QM/MM simulations. Activation parameters indicate the expected variation in activation energy and rate coefficient in aqueous phase in comparison to the gas phase. The shift of potential energy barrier through the... 

Ab initio molecular orbital calculations have been used to investigate the structures and the transition states of 1,3-dipolar cycloadditions between benzonitrile oxide with ethylene, cyclopentene, acrylonitrile and tetracyanoethylene in heptane and water: calculations reveal enhanced hydrogen bonding of a water molecule to the transition states for the cycloaddition 1,3-dipolar of reaction of benzonitrile oxide with cyclopentene, the optimal interaction energies being 0.7 kcal/mol more favourable for hydrogen bonding to the oxygen atom in the transition states than for the reactants  

Solute-solvent and solvent-solvent interactions were investigated for binary mixtures of an ionic liquid (IL) 2-hydroxy ethylammonium formate as with methanol, ethylene glycol and glycerol. The physicochemical properties of the solvent mixtures at 25 °C, over the whole range of mole fractions, were determined using solvatochromic probes. High normal polarity (ETN) in the alcohol-rich region confirms solute-solvent interactions in this medium. Dipolarity/polarizability (π *) show a different trend to ETN with a positive deviation from ideal behavior in IL-glycerol mixtures. However, these deviations for other solvent mixtures are insignificant. Contrary to what is observed for E TN and π*,... 

We demonstrate theoretically by density functional non-equilibrium Green's function method that a much simplest two-terminal wire can exhibit switching, and we present a realistic theory of its behavior. We consider a C20-bowl molecular wire sandwiched between an Au (1 0 0) substrate and a monatomic Au scanning tunneling microscope (STM) tip. Lateral motion of the tip over the pentagon ring causes it to change from one conformation class to the other and to switch between a strongly and a weakly conducting state. Thus, surprisingly, despite their apparent simplicity, these Au/C20/Au nanowires are shown to be a convenient switch, the simplest two-terminal molecular switches to date.... 

The heterogeneous environmentally friendly catalyst and photocatalyst based on Ag, Pt, Ag–Pt nanoparticles (NPs) loading on the γ-Fe2O3/CuO nanocomposite which was derived from Fe-metal organic framework (Fe-MIL-88B) and Cu-metal organic framework (Cu (tpa)) was introduced. The catalytic and photocatalytic activities of Ag–Pt loading on the γ-Fe2O3/CuO nanocomposite were performed for a reduction process (4-nitrophenol (4-Nip) to 4-aminophenol (4-Amp)), and decomposition organic dyes (AB92, MB) in the LED light. Metal-organic framework (MOFs) composed with inorganic and organic linker which used as suitable precursors to obtain different type of nanostructures for environmental applications.... 

In this work, the synthesis, characterization, and kinetic investigation of the free-radical polymerization of 4-acetylaminobenzene propenoic ester (ABPE) and 4-methylbenzene propenoic ester (MBPE) were studied. The kinetic behaviors of ABPE and MBPE in the polymerization initiated by azobisisobutyronitrile in dimethylformamide solutions at temperatures between 50 and 120°C were investigated, and experimental and theoretical conversion-time curves were compared. Both monomers showed a polymerization ceiling temperature (T c ). Tc was calculated with experimental values of k pk1/2 with a constant concentration of 0.7 mol/L for monomers. Tc was about 141 and 131 °C for ABPE and MBPE,... 

In this paper, we study the electrical transport and Negative Differential Resistance (NDR) in a single molecular conductor consisting of a cysteine sandwiched between two Au(111) electrodes via the Density Functional Theory-based Nonequilibrium Green's Function (DFT-NEGF) method. We show that (surprisingly, despite their apparent simplicity, these Au/cysteine/Au nanowires are shown to be a convenient NDR device) the smallest two-terminal molecular wire can exhibit NDR behavior to date. Experiments with a conventional or novel self-assembled monolayer (SAM) are proposed to test these predictions. The projected density of states (PDOSs) and transmission coefficients T(E) under various... 

TiO2 nanoparticles supported on activated carbon (AC) and multiwalled carbon nanotubes (MWCNTs) were prepared by the sol-gel method using ultrasonic irradiation. All the prepared samples were calcined at different temperatures and characterized by X-ray diffraction, nitrogen adsorption/desorption isotherms, scanning electron microscopy, transmission electron microscopy and diffuse reflectance spectroscopy. The effects of size and type of carbon on the morphology and photocatalytic activity of the resulting hybrid materials were investigated. The results showed that a decrease in the size of the carbon led to a decrease in size of TiO2 nanoparticles. Both AC and MWCNTs retarded the... 

Abstract A visible-light-active Ag3PO4/BiPO4 nanocomposite with a p-n heterojunction structure was fabricated via a co-precipitation hydrothermal process using 2-hydroxylethylammonium formate (RTIL) as a room-temperature ionic liquid. The resulting catalysts were characterized by various techniques. The photocatalytic activity of the photocatalysts was evaluated by the photodegradation of phthalocyanine Reactive Blue 21 (RB21) under both visible and UV light irradiations. The results reveal that the heterojunction composite prepared in RTIL noticeably exhibited an improvement in both efficiency and rate of RB21 photodegradation in comparison with pure Ag3PO4 and BiPO4. The enhanced... 

In this work, PtxPd1-x (x = 0, 0.5, and 1)nanoparticles (NPs)were synthesized on the surface of SiO2@graphene oxide which covered by 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF6)ionic liquid (IL)layer. FT-IR spectroscopy, zeta potential, CHN elemental analysis, XRD, XPS, SEM, EDX, TEM, TGA, BET, and ICP-AES techniques were applied for the characterization of the multiphasic catalyst. The as-prepared nanocomposite was used as an effective heterogeneous catalyst for the oxidation of cyclohexene by molecular oxygen, as a green oxidant. Different experimental conditions such as oxygen pressure, reaction time, reaction temperature and amount of catalyst were investigated in this... 

One of the appealing usages of metal–organic frameworks is their application in manufacturing of metal oxide and metal oxide nanocomposites. In the present study, we used zeolitic imidazolate framework (ZIF-8) as precursor to prepare a new Ag/C/ZnO catalyst. The as-prepared samples were characterized using X-ray diffraction, Fourier-transform infrared, scanning electron microscopy and transmission electron microscopy analysis. Improved catalytic performance of as-prepared Ag/C/ZnO was confirmed by reduction of organic pollutants including p-nitrophenol, methylene blue and rhodamine-B in the presence of NaBH 4 in aqueous media. The synergistic effect between Ag and ZnO was proposed as the... 

In present study, an efficient method was used to synthesis Au and Pt nanoparticles on Ni modified MoS2 (MNi/MoS2 (M = Au and Pt). The morphology and structure of the prepared products were characterized using different microscopic and spectroscopic methods. The as-synthesized MNi/MoS2 nanocomposites were applied for catalytic reduction of p-nitrophenol (P-NP) in the presence of NaBH4. P-NP is one of the prevalent contaminants in wastewaters, while its corresponding aromatic amine (4-aminophenol) is a precious intermediate for manufacturing of important materials such as pharmaceuticals. The obtained catalytic results indicated that noble metal nanoparticles significantly affect catalytic... 

A combination of the experimental and theoretical study was carried out on the reaction mechanism associated with the pyrolysis of 2-pyridylacetic acid in the gas phase. Methylpyridine and carbon dioxide were analyzed as the products, using a static system over the pressure range of 18-55 torr and the temperature of 541.2-583.4 K. The experimental kinetic data show that the pyrolysis process is homogeneous, unimolecular and proceeds through a concerted mechanism. Theoretical studies at the B3LYP level using the 6-31G* basis set confirmed an asynchronous concerted mechanism for the reaction. Computed kinetic and activation parameters are in good agreement with the experimental one. © 2006... 

Fe3O4 magnetic structure was synthesized with co-precipitation method. Surface of magnetic core was modified with hydrophobic BMIM[PF6] ionic liquid. The samples became antibacterial by loading gold, copper and silver nanoparticles and denoted as Fe3O4/IL/X (X=Ag, Au, Cu). X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), thermal gravimetric analysis (TGA), Atomic absorption spectroscopy (AAS), Fourier transform infrared (FTIR) and vibration sample magnetometer (VSM) technics were applied for catalysts characterization, metal concentration analysis and morphology monitoring. Modified nanostructures were used for inactivation of Escherichia coli as... 

A combined experimental and computational study was carried out on the gas phase pyrolysis reaction of diallylsulfoxide. Allylalcohol and Thioacrolein were detected as the major products during a unimolecular reaction. Experimental kinetic studies were carried out via a static system over the pressure of 21-55 torr and temperature of 435.2-475.1 K. Based on the experiments, the reaction is homogeneous and proceeds through a zwitterionic intermediate. Computational studies at the DFT (B3LYP) and QCISD(T) levels with 6-311++G(d,p) basis set indicated a two-step concerted pathway as the possible route. Comparison between the experimental and theoretical activation parameters for the most... 

Functionalized magnetic core–zeolitic shell nanocomposites were prepared via hydrothermal and precipitation methods. The products were characterized by vibrating sample magnetometer, X-ray powder diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption–desorption isotherms, and transmission electron microscopy analysis. The growth of mordenite nanocrystals on the outer surface of silica-coated magnetic nanoparticles at the presence of organic templates was well approved. The removal performance and the selectivity of mixed metal ions (Pb2+ and Cd2+) in aqueous solution were investigated via the sorption process. The batch method was employed to study the sorption kinetic,...