Palladium Nanohexagons and Nanospheres in Selective Alkyne Hydrogenation

Palladium nanohexagons were prepared using a seed-mediated method. Their catalytic performance in 2-methyl-3-butyn-2-ol hydrogenation was compared to the one of monodispersed Pd nanospheres. Quantitative correlations between initial turnover frequencies (TOFs) and nanoparticle surface compositions showed independence of TOFs calculated per atoms on Pd(111) facets on particle size and shap

Shape and Size-Tailored Pd Nanocrystals to Study the Structure Sensitivity of 2-Methyl-3-butyn-2-ol Hydrogenation: Effect of the Stabilizing Agent

Uniform Pd nanocrystals of cubic, octahedral and cube-octahedral shapes were synthesized via a solution-phase method using two stabilizers: poly (vinyl pyrrolidone) (PVP) and di-2-ethylhexylsulfoccinate (AOT) and tested in the hydrogenation of 2-methyl-3-butyn-2-ol. The AOT-stabilized Pd nanocrystals were found to be an order of magnitude more active, but less selective than those stabilized by PVP. This could be attributed to a stronger interaction of PVP with surface Pd by adsorbed N-containing groups. The results obtained were rationalized applying a two-site Langmuir-Hinshelwood kinetic model that allowed predicting 3-4nm cubic or octahedral nanocrystals stabilized by AOT as the optimum active phase ensuring the highest production rate of target MB

Novel Catalytic Dielectric Barrier Discharge Reactor for Gas-Phase Abatement of Isopropanol

Catalytic gas-phase abatement of air containing 250ppm of isopropanol (IPA) was carried out with a novel dielectric barrier discharge (DBD) reactor with the inner catalytic electrode made of sintered metal fibers (SMF). The optimization of the reactor performance was carried out by varying the voltage from 12.5 to 22.5kV and the frequency in the range 200-275Hz. The performance was significantly improved by modifying SMF with Mn and Co oxide. Under the experimental conditions used, the MnO x /SMF showed a higher activity towards total oxidation of IPA as compared to CoO x /SMF and SMF electrodes. The complete destruction of 250ppm of IPA was attained with a specific input energy of ∼235J/L using the MnO x /SMF catalytic electrode, whereas, the total oxidation was achieved at 760J/L. The better performance of the MnO x /SMF compared to other catalytic electrodes suggests the formation of short-lived active species on its surface by the in-situ decomposition of ozon

Intensification of slow reversible chemical transformation: carboxylation of resorcinol as a case study

Conjugated kinetic and thermodynamic modeling is suggested as a suitable approach to identify a novel process window (NPW) for the intensification of slow reversible reactions. The aqueous Kolbe-Schmitt synthesis of β-resorcylic acid is taken as a model. The potential of operating at high pressure (P) and temperature (T) is evaluated in order to reduce the characteristic reaction time (tr) and increase the specific productivity. For the first time, a reliable kinetic model for this reaction is derived from batch experiments. Based on this model, an NPW of P=10 bars, T=453 K is determined for a continuous reactor operated at a residence time of 28 s. It is predicted that the specific productivity can be increased by a factor of 100 with a 4.2 times less concentrated KHCO3 solution, as compared to a conventional batch process, if the reaction is kinetically controlled. The model prediction is experimentally validated with a continuously operated milli-reactor equipped by SMXS mixer elements (Sulzer Chemtech, Switzerland) ensuring a fast mixing (characteristic mixing time ~4.10-2 s). The milli-reactor renders exclusively β-resorcylic acid (selectivity 100%) and confirms process intensification (PI) of two orders of magnitude as compared to conventional batch operatio

Palladium Nanohexagons and Nanospheres in Selective Alkyne Hydrogenation

Palladium nanohexagons were prepared using a seed-mediated method. Their catalytic performance in 2-methyl-3-butyn-2-ol hydrogenation was compared to the one of monodispersed Pd nanospheres. Quantitative correlations between initial turnover frequencies (TOFs) and nanoparticle surface compositions showed independence of TOFs calculated per atoms on Pd(111) facets on particle size and shape

Detoxification of diluted azo-dyes at biocompatible pH with the oxone/Co2+ reagent in dark and light processes

Accelerated bleaching and photobleaching of diluted solutions of Methyl Orange and other dyes occur only when Co2+-ions are present in solution mediating oxone (2KHSO(5)center dot KHSO4 center dot K2SO4) decomposition. The bleaching of Methyl Orange, Orange II and Methylene Blue dyes in dilute solutions (0.01 mM) proceeds within a few minutes and occurs at biocompatible pH leading to a decrease in the toxicity of the initial solution under simulated daylight radiation. A reduction in the toxicity of 35% was observed at biocompatible pH-values when a solution Orange II (0.01 mM) was irradiated in the presence of oxone (0.06 mM)/Co2+ (0.004 mM). Only traces of Co2+ were necessary to accelerate the decomposition of the dyes in the presence of oxone in the dark and even more under daylight irradiation. The photobleaching proceeds with a photonic efficiency of similar to 0.24. The solution parameters were optimized for the photobleaching of azo-dyes by the oxone/Co2+ reagent. H2O2 generation was observed to be possible only as long as Orange II was present in the solution. The decomposition kinetics of H2O2 was followed under solar radiation. The dye decomposition was also investigated as a function of the applied light intensity. No saturation effects were observed when simulated solar light with 90% AM1 was applied. The photobleaching reaction proceeded with acceptable kinetics with light intensities 5-10 times lower than AM1. This makes the photocatalytic treatment suitable under diffuse daylight. (c) 2006 Elsevier B.V. All rights reserved

Recent Advances in the Liquid-Phase Synthesis of Metal Nanostructures with Controlled Shape and Size for Catalysis

Recent advances in the liquid-phase synthesis of metal nanostructures of different sizes and shapes are reviewed regarding their catalytic properties. The controlled synthesis of nanostructures is based on the colloid chemistry techniques in the solution, which use organic nanoreactors and a variety of stabilizers. Their catalytic activity and selectivity depend on the particle’s shape and size, as shown for Suzuki and Heck coupling, hydrogenations, hydrogenolysis, oxidations, and electron-transfer reactions. The knowledge of a reaction’s structure-sensitivity relationship is important for the rational catalyst design in view of process intensification. Nanostructures can be used per se and in supported form to meet the requirements of an eventual process

Catalytic activity of FeZSM-5 zeolites in benzene hydroxylation by N2O: The role of geometry characterized by fractal dimensions

The fractal dimensions of FeZSM-5 zeolites were used to characterize the change in their geometry depending on different post-synthesis treatments. The fractal dimension values were estimated from the Dubinin-Astakhov isotherms of nitrogen adsorption and related to the activity of these zeolites in the benzene hydroxylation to phenol by nitrous oxide. The zeolites had two different iron contents (350 and 5800 ppm) and a Si/Al ratio of 42. The catalysts were activated by steaming (823 K) and/or calcinations in He (1323 K). The FeZSM-5 activated by steaming exhibited fractal dimensions lower than the samples activated by calcinations. The steamed samples also had activities in the benzene hydroxylation per Fe(II) site (TOF values) somewhat higher as compared to the zeolites activated by calcinations. This indicates the importance of the zeolite geometry for the reaction of bulky benzene molecule within a confined space. (c) 2005 Elsevier B.V. All rights reserved

Microstructured reactors for catalytic reactions

A review. This review addresses the catalytic reactions performed in microstructured reactors, which are more and more recognized in recent years as a novel approach for chem. and chem. process industry. They are particularly suited for highly exothermic and fast reactions allowing temp. control and isothermal operation. A brief evaluation of the advantages for gas-phase, liq.-phase, and gas-liq.-solid reactions carried out in miniaturized devices is discussed. Alternative designs to achieve microstructured fluid patterns, besides microfabrication, are also described. [on SciFinder (R)