Mesoporous material as catalyst for the production of fine chemical: Synthesis of dimethyl phthalate assisted by hydrophobic nature MCM-41

Aluminum, iron and zinc containing MCM-41 molecular sieves were prepared by the hydrothermal method. The catalyst was characterized by the XRD, BET (surface area), FT–IR and ²⁹Si, ²⁷Al MAS–NMR techniques. The catalytic activity of these molecular sieves was tested with esterification reaction used with phthalic anhydride (PAH) and methanol (MeOH) in the autoclave at 135 °C, 150 °C and 175 °C. Conversion increases with an increase in temperature and mole ratio. The activity of these catalysts followed the order: Al-MCM-41 (112) > Fe-MCM-41 (115) > Al-MCM-41 (70) > Al-MCM-41 (52) > Fe-MCM-41 (61) > Al, Zn-MCM-41 (104) > Al-MCM-41 (30). The reaction yielded both monomethyl phthalate (MMP) and dimethyl phthalate (DMP). The nature of the catalyst sites has been proposed using with water as an impurity. The selectivity of the dimethyl phthalate increases with increase in temperature and mole ratio. The weight of the catalyst was optimized at 0.07 g. The hydrophilic and hydrophobic nature of the catalyst has been explained by the influence of water and the external surface acidity also facilitates the reaction and this has been confirmed by the supporting reaction.     

Synthesis of activated carbon foams with high specific surface area using polyurethane elastomer templates for effective removal of methylene blue

Carbon foams have gained significant attention due to their tuneable properties that enable a wide range of applications including catalysis, energy storage and wastewater treatment. Novel synthesis pathways enable novel applications via yielding complex, hierarchical material structure. In this work, activated carbon foams (ACFs) were produced from waste polyurethane elastomer templates using different synthesis pathways, including a novel one-step method. Uniquely, the produced foams exhibited complex structure and contained carbon microspheres. The ACFs were synthesized by impregnating the elastomers in an acidified sucrose solution followed by direct activation using CO₂ at 1000 ℃. Different pyrolysis and activation conditions were investigated. The ACFs were characterized by a high specific surface area (S_BET) of 2172 m²/g and an enhanced pore volume of 1.08 cm³/g. Computer tomography and morphological studies revealed an inhomogeneous porous structure and the presence of numerous carbon spheres of varying sizes embedded in the porous network of the three-dimensional carbon foam. X-ray diffraction (XRD) and Raman spectroscopy indicated that the obtained carbon foam was amorphous and of turbostratic structure. Moreover, the activation process enhanced the surface of the carbon foam, making it more hydrophilic via altering pore size distribution and introducing oxygen functional groups. In equilibrium, the adsorption of methylene blue on ACF followed the Langmuir isotherm model with a maximum adsorption capacity of 592 mg/g. Based on these results, the produced ACFs have potential applications as adsorbents, catalyst support and electrode material in energy storage systems.     

Coupling RSM with soot model for the study of soot formation in a momentum-dominated strained jet flames

Journal of Thermal Analysis and Calorimetry - This paper presents a comparison between the numerically determined soot volume fraction (SVF) in a momentum-dominated turbulent diffusion strained jet...     

Transformation of a 4-membered ring zinc phosphate SBU to a sodalite-related 3-dimensional structure through a linear chain structure

A zero-dimensional zinc phosphate, comprising a 4-membered ring, is shown to spontaneously transform at room temperature, to a linear chain structure consisting of corner-shared 4-membered rings, the latter transforming to a 3-dimensional sodalite-related structure under mild conditions.     

聚合物负载的钯-咪唑催化烯烃加氢

A polymer-supported palladium-imidazole catalyst was used to catalyze the hydrogenation of various olefins under mild conditions. The rate of hydrogenation was studied. The effects of factors such as substrate concentration,catalyst concentration,partial pressure of hydrogen and temperature on initial rate of reaction of selected olefins were investigated. A mechanism for the reaction was proposed from the rate equation. The effects of the solvent and structure of the olefin on the rate of hydrogenation were investigated. The catalyst showed good reusability without any leaching of metal from the support. The homologous analog of the polymer-supported catalyst could not be used as catalyst for the hydrogenation of olefins in methanol because there was precipitation of the metal during reaction.     

Third-order nonlinear optical studies of newly synthesized polyoxadiazoles containing 3,4-dialkoxythiophenes

The third-order nonlinear optical properties of newly synthesized soluble polyoxadiazoles containing 3,4-dialkoxythiophenes were investigated by using Z-scan and degenerate four-wave mixing (DFWM) techniques. The measurements were performed at 532 nm with 7 ns pulses from a Nd:YAG laser. We found a good agreement between the values of χ⁽³⁾ determined from both the experiments. Z-scan results indicate a negative nonlinear refractive index, n₂, whose magnitude is of the order of 10⁻¹⁰ esu for all the copolymers. The variation of nonlinear response among the copolymers clearly indicates the dependence of χ⁽³⁾ on donor and acceptor type of units present in these copolymers. The copolymers exhibit strong reverse saturable absorption and good optical limiting properties at 532 nm.     

Catalytic activity of a supported palladium–benzimidazole complex toward alkene hydrogenation

A polymer anchored palladium complex was synthesized by sequential attachment of benzimidazole and palladium chloride to chloromethylated polystyrene divinyl benzene co-polymer with 6.5 % cross-linking. The product was characterized by XPS, UV–vis. spectrophotometry, FTIR and TGA. Various physico-chemical properties such as bulk density, surface area and swelling behavior in different solvents were also measured. The polymer anchored complex was tested as a catalyst for reduction of olefins. The kinetics of hydrogenation of 1-hexene was studied by varying the temperature, catalyst concentration and substrate concentration. The energy and entropy of activation were evaluated from the kinetic data. The catalyst could be recycled a number of times and no leaching of metal from the catalyst surface was observed.     

Synthesis and characterisation of a polymer-bound rhodium-benzimidazole complex as catalyst for the hydrogenation of nitroarenes

A polymer-anchored rhodium complex was synthesised by sequential attachment of benzimidazole (BzlH) and RhCl₃ to chloromethylated poly(styrene–divinylbenzene) co-polymer (PSDVB) with 6.5% cross-linking. The catalyst was characterised by X-ray photoelectron spectroscopy, far-IR, UV–Vis, FTIR, SEM and thermogravimetric analysis. Various physico-chemical properties such as bulk density, surface area and swelling behaviour in different solvents were also studied. The polymer-anchored complex was tested as a catalyst for reduction of nitroarenes, namely o,m,p-nitrobenzoic acid, nitroaniline, nitrophenol and nitrotoluene. Kinetic measurements were carried for o-nitroaniline and p-nitrophenol by varying temperature, catalyst concentration and concentration of substrates. The rate of the reaction was found to be first order with respect to catalyst concentration and also with substrate concentration at low concentrations, becoming independent of substrate at higher concentrations. A plausible mechanism for the reaction is proposed. The energy and entropy of activation calculated from Arrhenius plots indicate high activity of the catalyst on the support. The recycling efficiency of the catalyst has been studied and there was no leaching of metal from the catalyst surface.     

Relationship between 18O enrichment in leaf biomass and stomatal conductance

Models that explain the oxygen isotope enrichment in leaf water (and biomass) treat the relationship between the kinetic fractionation that occurs during evapotranspiration and the stomatal conductance in an empirical way. Consequently, the isotopic enrichment is always predicted to decrease with increasing stomatal conductance, regardless of the experimental evidence to the contrary. We explain why and suggest an alternative method to reconcile theory and experiment. We support this with our experimental data on rice and groundnut plants.     

An LC-ESI-MS method for the quantitative analysis of bile acids composition in fecal materials

In this work, a liquid chromatography coupled with electrospray ionization mass spectrometry (LC-ESI-MS) method was developed and validated for quantification of bile acids in fecal materials. Co-eluting matrix impurities in fecal materials have been shown to greatly suppress the ionization of analytes in mass spectrometry, which is known as the matrix effect. To correct large quantitative errors caused by the matrix effect, we developed a scheme that combined the standard addition method with internal standard (SA-IS). The fecal sample pretreatment involved a single step of extraction with ethanol. Bile acids were separated using a Luna C(18) column (150 mm, 2 mm i.d., 5 μm) with gradient elution. The deprotonated analytes were detected in selective ion monitoring mode. Our results showed that, by using this method, the accuracy of quantification was significantly improved in comparison to the conventional internal standard method. The linearity, sensitivity, accuracy and precision of the method were within the range of 0.05-5 μmol/L. This SA-IS method was successfully applied to the analysis of bile acids in the samples collected from patients diagnosed with inflammatory bowel disease.