Sharif Digital Repository

For the first time, the mechanism of Fischer esterification between acetic acid and ethanol over silica-functionalized propylsulfonic acid (silica-propyl-SO3H) catalyst was explored by means of computational modeling techniques. For this purpose, 6-edge-atom cage-like cluster comprising Si-O-Si sequences has been selected to represent the surface of the catalyst. The results indicate that the reaction goes through concerted transition states. In all optimized structures no proton (H+) transfer occurs from catalyst to the substrates and the role of the catalyst is via the activation of the substrates through the formation of strong hydrogen bonds (H-bonds). Furthermore, the energetic diagram... 

4H-chromenes play a significant role in natural and pharmacological products. Despite continuous advances in the synthesis methodology of these compounds, there is still a lack of a green and efficient method. In this study, we have designed cysteic acid chemically attached to magnetic graphene oxide (MNPs·GO-CysA) as an efficient and reusable solid acid catalyst to synthesize 4H-chromene skeletons via a one-pot three components reaction of an enolizable compound, malononitrile, an aldehyde or isatin, and a mixture of water–ethanol as a green solvent. This new heterogeneous catalyst provides desired products with a good to excellent yield, short time, and mild condition. This procedure... 

A novel magnetic Br∅nsted acid catalyst was synthesized based on growing poly(amidoamine) dendrimers on the surface of magnetic nanoparticles. After the dendronizing process, the MNP coated PAMAM was functionalized by chlorosulfuric acid to form an acid catalyst. Because of dendrimer coating of MNPs, catalyst shows good loading level of acidic groups on the surface. Also zwitterion nature of catalyst surface improves the catalytic activity. This new catalyst is proven to be highly effective in the synthesis of α-aminophosphonate compounds in a green way  

A functionalized poly(ionic liquid) coated magnetic nanoparticle (Fe 3O 4@PIL) catalyst was successfully synthesized by polymerization of functionalized vinylimidazolium in the presence of surface modified magnetic nanoparticles. The resulting heterogeneous catalyst is shown to be an efficient acidic catalyst for synthesis of 1,1-diacetyl from aldehydes under solvent free conditions and room temperature in high yields. Also, the catalyst shows good activity for the deprotection reaction of acylals. After completion of reaction, the catalyst was simply recovered by an external conventional magnet and recycled without significant loss in the catalytic activity. Because of the polymer layers... 

A two-stage thermocatalytic upgrading process using a novel catalyst was investigated to produce light olefins and liquid fuels from fuel oil. The upgraded oil from the first thermal stage demonstrated lower viscosity and higher crackability compared to the virgin feedstock. In the next step, the vapor-phase catalytic cracking of the upgraded fraction was implemented over a novel nanoporous composite catalyst, characterized by the XRD, FTIR, NH3- TPD, and N2 physisorption techniques. In total, more than 55 wt% of light olefins, particularly propylene (25.5 wt%) together with 25.4 wt% and 32.5 wt% of gasoline and diesel fuel were obtained in this process. © 2019, © 2019 Taylor & Francis... 

The acetylation of phenols with acetic anhydride proceeded in excellent yields when it was catalyzed by gadolinium triflate immobilized on magnetically recyclable nanocomposites. This heterogeneous catalyst provided high catalytic activity with low loading level (1 mol%), because the Lewis acid catalyst was grafted on the surface of the nanocomposites. The catalysts were also easily recovered from the reaction mixture using a magnet and reused for six consecutive cycles  

Palladium catalysts supported on functionalized multi-wall carbon nanotubes were synthesized for hydro-purification of crude terephthalic acid containing 2100ppm 4-carboxybenzaldehyde (4-CBA) as impurity. PdCl2 and Pd(OAc)2 were used as precursors. Palladium loadings were 0.05 to 0.6wt.% with catalysts reduced at 200 to 400°C. Catalysts prepared from both precursors with least 0.3wt.% palladium resulted in 99%+ removal of 4-CBA. The most desired selectivity was obtained for the catalyst with PdCl2 as precursor, reduction temperature of 300°C, and palladium loading of 0.3wt.%. This catalyst had slightly better performance than the commercial catalyst (0.5wt.% of palladium on activated carbon)... 

1-Butyl-3-methylimidazolium tungstate ([BMIm] 2WO 4) ionic liquid supported onto silica sulphamic acid demonstrated desirable performance for oxidation of cyclohexene to adipic acid. Simple experimental procedure, easy product isolation, catalyst recovery and reusability are some attractive features of this protocol  

The optimization of leaching parameters for the Ni recovery of the used catalyst was developed using response surface methodology. The relationship between the Ni recoveries, and four main leaching parameters, temperature, acid concentration, leaching time and particle size were presented as empirical model equations. The predicted values of nickel recoveries were found to be in a reasonable agreement with the experimental values, with R2 as correlation factor being 0.9669 and 0.9869 for sulfuric and nitric acids, respectively. The model equations were then optimized using the quadratic programming method to maximize nickel recovery. The optimum conditions were found to be 103.4°C... 

Palladium catalysts supported on functionalized multi-wall carbon nanotubes were synthesized for hydro-purification of crude terephthalic acid containing 2100ppm 4-carboxybenzaldehyde (4-CBA) as impurity. PdCl2 and Pd(OAc)2 were used as precursors. Palladium loadings were 0.05 to 0.6wt.% with catalysts reduced at 200 to 400°C. Catalysts prepared from both precursors with least 0.3wt.% palladium resulted in 99%+ removal of 4-CBA. The most desired selectivity was obtained for the catalyst with PdCl2 as precursor, reduction temperature of 300°C, and palladium loading of 0.3wt.%. This catalyst had slightly better performance than the commercial catalyst (0.5wt.%... 

A dual acidic heterogeneous organocatalyst was synthesized by copolymerization of acidic ionic liquid monomer (vinyl-3-(3-sulfopropyl) imidazolium hydrogen sulfate [VSim][HSO 4]) and ionic liquid crosslinker (1,4-butanediyl-3,3′-bis-l-vinyl imidazolium dihydrogen sulfate). The resulting ionic heterogeneous catalyst is shown to be an efficient dual acidic organocatalyst for synthesis of dihydropyrimidines using the Biginelli synthetic route under mild reaction conditions in high yields. Since monomers make the catalyst bed, crosslinked poly(ionic liquid) will have high loading level of acidic groups comparing to other heterogeneous acid catalysts. Despite of conventional heterogeneous ionic... 

The pK a of an acyclic aliphatic heptaol ((HOCH 2CH 2CH(OH)CH 2) 3COH) was measured in DMSO, and its gas-phase acidity is reported as well. This tertiary alcohol was found to be 10 21 times more acidic than tert-butyl alcohol in DMSO and an order of magnitude more acidic than acetic acid (i.e., pK a = 11.4 vs 12.3). This can be attributed to a 21.9 kcal mol -1 stabilization of the charged oxygen center in the conjugate base by three hydrogen bonds and another 6.3 kcal mol -1 stabilization resulting from an additional three hydrogen bonds between the uncharged primary and secondary hydroxyl groups. Charge delocalization by both the first and second solvation shells may be used to facilitate... 

Palladium nanocatalysts supported on reduced graphene oxide (rGO), multi walled carbon nanotubes (MWCNT), and rGO/CNT composite were synthesized by a wet impregnation method using PdCl2 as a precursor. Palladium loading was 0.3 wt %, and the catalysts were reduced at 300°C. The catalysts were characterized by inductively coupled plasma, Brunauer-Emmett-Teller (BET) analysis, Fourier transform infrared spectroscopy, X-ray powder diffraction, transmission electron microscopy, temperatue-programmed reduction, temperatue-programmed desorption, and Raman spectroscopy. The performance of the catalysts was investigated for hydro-purification of crude terephthalic acid (CTA) containing... 

The deactivation of solid acid catalysts in liquid phase alkylation of isobutane with 2-butene was investigated. Since under liquid phase conditions the alkylation reaction is severely diffusion limited, effects of diffusion on the rate of reaction and deactivation pathways were considered. In the present work, an attempt has been made to implement more appropriate assumptions in order to properly model catalyst deactivation in a mixed reactor. Accordingly, spatial variation of diffusivity in the pores of the catalyst was considered as a function of time on stream. The effect of the pore mouth plugging was also investigated and it was found that this phenomenon had a pronounced effect on the... 

Conjugated Linoleic Acid (CLA) was produced from castor oil using washed cells of Lactobacillus plantarum PTCC 1058 and Lactobacillus plantarum subsp. plantarum PTCC1745 as the catalyst. Under the optimal reaction conditions, the washed cells of Lactobacillus plantarum PTCC1058 produced 1661.26 mg of CLA/L reaction mixture (36% yield of production) from 4.6 mg/ml of castor oil after using 15% (w/v) cell for 121 h. The resulting CLA was a mixture of two CLA isomers, cis-9, trans-11 (or trans-9, cis-11)-octadecadienoic acid (CLA1, 44% of total CLA) and trans-10, cis-12-octadecadienoic acid (CLA2, 46% of total CLA). The total production of CLA is extracellular in all of the reactions performed... 

The catalytic activity of a mixture of ZnCl2: AlCl3 supported on silica gel was evaluated for the alkylation of phenols with benzyl alcohol, tret-butyl alcohol and styrene under microwave irradiation and solvent-free conditions. The catalyst preparation method, its characterization and reusability, were reported. The effect of the phenol to benzyl alcohol ratio and the time of reaction on the phenol conversion and distribution of products was investigated. A conversion percentage up to 97% was achieved when hydroquinone was used. A selective ortho- directed alkylation for phenol, α-naphthol and β-naphthol was observed. © Sharif University of Technology, December 2009