Sharif Digital Repository

In this thesis, ionic liquids and polymeric ionic liquids were investigated as solvent and support for immobilization of molybdenum and palladium catalysts. Three newly synthesized room temperature ionic liquids containing molybdate anion, [DMIm][MoO2(NCS)4], [RPy][MoO2(NCS)4] (R = butyl or decyl), and previously reported [BMIm][MoO2(NCS)4] were used as catalysts for the reduction of sulfoxides. For facilitating the recyclability of the catalysts, the ionic liquid solvents, [RMIm][PF6] and [RPy][PF6] (RMIm=1-n-alkyl-3-methylimidazolium, RPy= 1-n-alkylpyridinium), were applied to immobilize molybdenum catalysts. These catalysts showed high catalytic activity for sulfoxide reduction in this... 

In this project a new molybdenum (VI) complex with tetradentate Schiff base ligand which was soluble in water was synthesized and characterized. In the first step of ligand synthesis, the reaction was performed between salicylaldehyde and aniline, and then used concentrated sulfuric acid for sulfonation. In the next step 5- sulfosalicylaldehyde sodium salt was formed by removing of aniline with heating and using sodium carbonate. In the presence of ethylendiamine and bis (acetylacetonato) dioxomolybdenum(VI) the final product, cis-dioxo sodium (N,N-bis (5-sulfonatosalicyldene)1,2-diaminoethane) molybdenum (VI) complex was synthesized. The complex was characterized by (CHN) elemental... 

In the contest of conversion of water to hydrogen and oxygen there is a need for catalysts which will effectively support the oxidation of water. In nature, photosystem II relies on manganese for the oxidation of water. The water oxidizing complex (WOC) contains a cluster of four manganese atoms. In the past few years, there has been a tremendous surge in research on the synthesis of various manganese compounds aimed at simulating WOC of PS II. In this project, several manganese oxides as heterogeneous catalysts in water oxidation have been synthesized and characterized by FT-IR, X-ray diffraction, TGA, XPS, SEM and BET. Some of these oxides are able to oxidize water in the presence of... 

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... 

In this thesis, heterogenous catalysts based on magnetic nanoparticles were synthesized. In these catalysts, magnetic nanoparticles were coated with defferent fuctional groups to produce a catalyst with magnetic properties which is easily separated from the reaction medium. The structure of synthesized catalyst was characterized using techniques such as transmission electron microscopy (TEM), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), and CHNS elemental analysis. Easy preparation, low cost, biodegradability and high thermal stability are advantages of these catalysts. At the end, the catalytic properties of resulted catalysts were investigated in many... 

Bread scraps with transition metals oxides spinels have been utilized to synthesize¬ magnetic nanocatalyst. The heterogeneous catalyst was characterized using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). The reaction was performed for tandem Knoevenagel-Micheal reaction in the presence of synthesized nanocatalyst as a heterogeneous, environmentally benign, cost-effective catalyst with high catalytic activity using EtOH as a green solvent. The magnetic nanocatalyst was applied to synthesize tetraketones and pyranopyrazoles... 

Three Keggin-type heteropolyacids were impregnated upon halloysite to produce heterogeneous acidic catalysts for synthesizing 5-hydroxymethylfurfural (5-HMF). Comparing the effectiveness of variously prepared catalysts in producing 5-HMF from fructose revealed the important role of halloysite in the final catalyst's acidic properties and performance in the reaction of halloysite-supported silicotungstic acid. Adjusting the reaction parameters for obtaining optimal results for the catalyst of choice was conducted via Response Surface Methodology and it was found that use of catalyst with 11 wt.% active ingredient at 125 °C in DMSO solvent yielded the target compound with 99.5% after 43 min.... 

The magnetic MOF-based catalytic system has been reported here to be an efficient catalyst for running CDC reactions and synthesis of Triazole rings under optimal conditions. The robust MOF catalyst was built based on magnetic nanoparticles and HKUST-1 which further modified with thioacetamide and carbonization. The catalyst structure was confirmed by various techniques. Furthermore, the products’ yields were obtained in good to excellent for all reactions under mild conditions which result from superior activity of the synthesized heterogeneous catalyst containing Cupper. Also, the magnetic property of the MOF-based catalyst makes it easy to separate from reaction mediums and reuse in the... 

In this research, synthesis of new heterogeneous catalysts has been studied. These catalysts were prepared in three different areas of the synthesis of coordination polymers and metal-organic frameworks, supported palladium nanoparticles on these polymers, and production of metal oxide nanoparticles. At first, metal organic frameworks of cobalt and manganese transition metals were synthesized through hydrothermal method. In order to prepare these frameworks, 1,4-benzenedicarboxylic acid (terephthalic acid) and 2-amino-1,4-benzenedicarboxylic acid ligands were utilized as spacer ligands. X-ray analysis indicated that the structure of polymers is composed of secondary building units (SBUs) of... 

Nowadays, the use of microreactors is receiving a great deal of attention due to the unique characteristics of such systems, such as high surface-to-volume ratio, low material loss, greater safety, and minimizing mass and heat transfer limitations. In this study, the optimization of the continuous-flow synthesis of Plavix by Cu-MOF heterogeneous catalyst utilizing a glass microreactor was investigated. Structural characteristics of the catalyst were investigated using X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), and BET surface area studies to describe the structure and morphology of the catalyst. In order to build... 

Two new copper(II) complexes, [CuL2] and [Cu(phox)2], were synthesized by reaction of 1-((4-bromophenylimino)methyl)naphthalen-2-ol, HL, and 2-(2′-hydroxyphenyl)-2-oxazoline, Hphox, as ligands and copper(II) acetate mono-hydrate with the ratio 2:1 (ligand:metal), respectively. For characterization and structure determination of synthesized complexes, different techniques were performed such as FT-IR, elemental analyses (CHN), and X-ray crystallography. The geometry around Cu atom is almost square planar in both complexes. The catalytic activity of the complexes was evaluated in azide–alkyne cycloaddition reaction in water without need of any additional agent. The reaction conditions for the... 

In this project a novel molybdenum(VI) complex with tridentate Schiff base ligand which is soluble in water was synthesized and characterized. In the first step of complex synthesis, chloromethylation of salicylaldehyde was carried out and then, corresponding pyridine salt prepared in the second step. Ligand N-[(3-pyridinium chloride) salicylidene]-2-aminophenol was formed by reaction with aminophenol. In the presence of MoO2(acac)₂ the final product, cis-dioxo(N- (3-pyridinumchloride)salicylidene]-2-aminophenolato)ethanol olybdenum(VI) complex synthesized. The complex was characterized by CHN elemental analysis and spectroscopic methods UV, NMR and FT-IR.We used a high-yield (80-98%) and... 

Epoxidation of alkenes by Mn(III)meso-tetra(4-sulfonatophenyl)porphyrin chloride (MnTPPS4Cl) in the various homogeneous and heterogeneous catalytic systems was investigated. In the case of homogeneous catalysis, epoxidation of cyclooctene in CH2Cl2/MeOH mixture using urea hydrogen peroxide (UHP) as an oxidant and imidazole as a co-catalyst results in the formation of cycloocetene oxide in 87% yield. Using this catalytic system various alkenes successfully oxidized to their corresponding epoxide in high conversions and selectivity. Cyclic alkenes oxidized more easily than linear alkenes. In addition, epoxidation of alkenes was investigated in the heterogeneous catalytic systems. For this... 

We have reported a new and efficient synthesis of tetrahydrothiopyrano [2,3-b]indole skeletons via unique tandem reaction of indoline-2-thiones to Baylis-Hillman adduct acetates. This protocol is a very mild and simple method for construction heterocycles in a one-step process. This is a convenient and diastereoselective synthesis of methyl 4-aryl-2,3,4,9-tetrahydrothiopyrano[2,3-b]indole-3-carboxylate systems in the presence of K2CO3 in acetonitrile. The major benefits of the current study are the one-pot procedure, high yields and diastereoselectivity, short reaction times and the similarity of the products to the biologically active moieties.
In addition 1, 4-diazabicyclo [2.2.2]... 

Water-gas shift reaction (CO(g) + H2O(g) ↔ CO2(g) + H2(g)) is performed as the key step in the hydrogen and ammonia industrial plant. In this work, Fe/Cr/Cu high temperature water gas shift catalysts were synthesized by coprecipitation method, using sulfate precursors, in order to improve the catalytic performance and particular emphasis is placed on the catalytic activity affected by aging time, precipitating agent and ways of increasing the mechanical strength. Finally the prepared and industrial catalysts were compared when they were situated in the operating conditions (at 360oC and 2 bar) and were characterized by BET, XRD, TPR, TEM and crushing strength analysis. Catalysts being made... 

Nowadays, heterogeneous photocatalytic processes have attained a particular importance among the other advanced oxidation processes in purification of organic polluted wastewaters. Titanium oxide is the most popular photocatalyst because of its strong oxidizing abilities for decomposition of organic pollutants, superhydrophilicity, chemical stability, long durability, non-toxic nature, and low cost. Same as other semiconductors, high recombination rate of charge carriers is the main weakness that cause decreases in photocatalytic efficiency. One of the solutions is coupling this material with other semiconductors. Core-shell nanoparticles are the type of these composites that show high... 

In the first section, due to the important role of nanocatalysts in different fields of chemistry, magnetic metal ferrite nanoparticles were synthesized. Ferrite nanoparticles were synthesized using co-precipitation method and were characterized. Then, these nanoparticles were applied as catalyst system for one-pot β-ketophosphonates and thiophosphate synthesis.This is a green and efficient route for S-P and C-P bond construction using copper ferrite nanoparticles as catalyst. The application of a highly active recyclable heterogeneous nanocopper ferrite catalyst for the oxyphosphorylation reaction of various alkenes was conducted under ligand-free conditions, in acetonitrile as solvent at... 

Silicon carbide due to its noticeable mechanical and thermal properties, uses in various industries either main substrate or reinforcement. SiC has low specific surface area according to its resistivity against sintering. Recently, a lot of scientists have been worked on SiC in order to fabricating small ones ; subsequently, better sintering will be achieved. Chemical vapor deposition method (CVD) is a method to produce fine SiC with deposition of products by reacting of initial materials from gas environment. In this study normal CVD as proper method and hydrogen, silicon tetrachloride and activated carbon as initial materials are chosen. Using of iron and nickel catalysts in temperature... 

This project evaluates the feasibility of using waste salmon fish bones as the reusable and low cost solid catalyst support for synthesis of biodiesel from waste sunflower oil via transestrification method. Calcinated waste fish bone derived hydroxyapatite (HAP) was employed as the supporter for KOH & K2CO3 to prepare an efficient solid base catalyst for biodiesel production. The catalyst were characterized by SEM-EDS, XRD, FTIR, BET, TGA, ICP. The effects of catalyst preparation conditions (such as fish bone and KOH or K2CO3 calcination temperature, loading of KOH or K2CO3 on the support), reaction conditions (such as reaction time, methanol/oil molar ratio, reaction temperature and... 

The aim of this study is developing and investigating heterogeneous catalysts based on natural calcite for the transesterification of canola oil and methanol in order to produce biodiesel as a renewable and alternative fuel for fossil fuels. At first calcite was calcined at high temperature to decompose calcium carbonate to calcium oxide. Afterward, Mg-Zr/CaO catalysts were prepared with mass ratio of 2:1 Mg:Zr and different weight percent(2.5, 5,7.5 and 10 wt%) on calcite supported by impregnation method. In order to characterized synthesized catalysts used different analysis such as energy dispersive X-ray (EDX) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy...