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showing 10 items of 13546 documents
Atomic Layer Deposition of Aluminum Oxide on TiO2 and Its Impact on N3 Dye Adsorption from First Principles
2011
The atomic layer deposition of aluminum oxide on an OH-terminated TiO2(101) anatase surface was studied employing density functional theory calculations. The formation of the Al2O3−TiO2 interface during the first atomic layer deposition cycle was modeled by studying the dissociative adsorption of an Al(CH3)3 precursor, followed with a H2O-pulse reaction step that changes the surface termination. Calculations provide evidence for the formation of a discontinuous, atomically rough aluminum oxide layer after the first cycle. To explore the role of the aluminum oxide layer on adsorption of a ruthenium-based N3 dye molecule, various adsorption geometries were investigated. Calculations show that…
Light-induced, site-selective isomerization of glyoxylic acid in solid xenon
2014
Abstract The isomerization of glyoxylic acid (GA) and its water complex was studied in a low temperature xenon matrix. The aim of these studies was to understand how xenon environment affects the cis-trans GA interconversion upon near infrared irradiation. In solid xenon, the GA conformers are embedded in two different matrix sites. These show up as different vibrational bands of GA that exhibit different kinetic rates of isomerization. Upon complexation with water, the isomerization process slows down. Xenon matrix appears not to affect energy relaxation process via intramolecular or intermolecular hydrogen bond as compared with previous experiments in an argon.
First Synthesis of β-Keto Sulfoxides by a Palladium-Catalyzed Carbonylative Suzuki Reaction
2005
[reaction: see text] An unprecedented palladium-catalyzed three-component cross-coupling reaction between alpha-bromo sulfoxide, carbon monoxide, and aromatic boronic acids provides a new and efficient approach to the synthesis of beta-ketosulfoxides. The reaction takes place under mild conditions with a wide range of variously substituted aryl and heteroaryl boronic acids. The carbonylative cross-coupling reaction is strongly favored over competing direct cross-coupling and homocoupling processes, except with boronic acids carrying strong electron-withdrawing substituents.
Nanopore charge inversion and current-voltage curves in mixtures of asymmetric electrolytes
2018
[EN] We consider the screening of the negative charges (carboxylic acid groups) fixed on the surface of a conical-shaped track-etched nanopore by divalent magnesium (Mg2+) and trivalent lanthanum (La3+). The experimental current (I)-voltage (V) curves and current rectification ratios allow discussing fundamental questions about the overcompensation of spatially-fixed charges by multivalent ions over nanoscale volumes. The effects of charge inversion or reversal on nanopore transport are discussed in mixtures of asymmetric electrolytes (LaCl3 and MgCl2 with KCl). In particular, pore charge inversion is demonstrated for La3+ as well as for mixtures of this trivalent ion at low concentrations …
Unprecedented Palladium-Catalyzed Cross-Coupling Reaction of α-Bromo Sulfoxides with Boronic Acids
2003
[reaction: see text] A new Suzuki-type palladium-catalyzed reaction of boronic acids with alpha-bromo sulfoxides has been developed using a protocol similar to the well-documented reaction of boronic acids with aryl halides. Both cross-coupling and homocoupling processes were observed. The best yields in cross-coupling products were obtained when the presence of oxygen was carefully excluded using degassed solvents. The oxidative addition palladium complex intermediate could be isolated and characterized by X-ray single-crystal diffraction.
Pd and PdAu on mesoporous silica for methane oxidation: Effect of SO2
2007
Abstract Palladium and gold–palladium catalysts supported on mesoporous silica were prepared by incipient wetness impregnation. They were characterized by XPS, XRD, BET, and FTIR acidity measurements. The activity was tested in the oxidation of methane under lean conditions. The effect of adding SO 2 to the reactant mixture was investigated. Test reactions were consecutively performed to evaluate the thermal stability and poisoning reversibility. The palladium catalyst performed quite well in terms of the light-off temperature ( T 50 300 °C) and SO 2 tolerance. Moreover, the activity, which decreased after a night treatment in SO 2 at 350 °C, was completely recovered in subsequent cycles. …
Decomposition of nitrous oxide upon nickel oxide-magnesium oxide solid solutions
1966
The decomposition of N 2 O has been studied over MgO catalysts, doped with NiO and NiO + Li 2 O from 1 to 10% (atomic). For pure MgO, activity is low, but is enhanced by addition of Ni 2+ ions. The apparent activation energy is reduced from 35 kcal/mole for pure MgO, to about 18 kcal/mole. Oxygen acts as a poison, and it is chemisorbed on the catalyst. The presence of lithium greatly increases the apparent activation energy. The results are interpreted in terms of oxygen chemisorption and of its influence on the course of the reaction.
Advances towards highly active and stereoselective simple and cheap proline-based organocatalysts
2010
Ten 4-acyloxy-L-prolines were screened as catalysts at loadings of 2–0.1 mol-% for the direct asymmetric aldol reaction in water by using variable amounts of water. Among them, a new catalyst, the L-proline carrying a trans-4-(2,2-diphenylacetoxy) group, and a catalyst previously synthesized by us, the L-proline carrying a trans-4-(4-phenylbutanoyloxy) group, were found to be excellent catalysts for the aldol reaction between cyclohexanone or cyclopentanone and substituted benzaldehydes when employed in only 1 and 0.5 mol-%,respectively, at room temperature without additives. For such catalysts, high turnover numbers were obtained, which are among the highest values obtained for enamine org…
Crystal structure of a CsF-uranyl-salen complex. An unusual cesium-chlorine coordination.
2006
Complexation of CsF with the ditopic uranyl-salen receptor results in a solid-state structure, in which the coordination sphere of cesium is filled by ligation to one of the chlorine atoms of the solvent chloroform. This X-ray structure is the first example of chloroform ligation to an alkali-metal ion.
Gold(I)-catalyzed intermolecular oxyarylation of alkynes: unexpected regiochemistry in the alkylation of arenes.
2009
The reaction between acetylenes and sulfoxides, studied as a test case for gold-catalyzed intermolecular addition, provides the oxyarylation compounds 3 in good yields. Unpredictably, in all cases a single regioisomer arising from the electrophilic aromatic alkylation at the position adjacent to the sulfur atom is obtained instead of the expected Friedel−Crafts regioisomer. A new concerted mechanism based on DFT calculations is proposed to account for the products in this intermolecular gold(I)-catalyzed reaction.