Search results for "HETEROGENEOUS CATALYSIS"
showing 10 items of 233 documents
A new class of heterogeneous Pd catalysts for synthetic organic chemistry
2011
A new series of leach-proof nanostructured Pd(0) catalysts able to catalyze a number of fundamental organic transformations including C–C bond formation has been developed. Reactions in general proceed with high yield and often at completion, while the catalysts can be reused in further reaction runs. This establishes a new class of relevant solid catalysts for synthetic organic chemistry trademarked SiliaCat Pd0 Hydrogel.
Thiazolium-based catalysts for the etherification reaction of benzylic alcohols under solvent-free condition
2015
Thiazolium and imidazolium hybrid materials were prepared by radical reactions between a mercaptopropyl-modified SBA-15 mesoporous silica and bis-vinylthiazolium or bis-vinylimidazolium dibromide salts. These hybrid materials were characterized by several techniques and were employed in the etherification reaction of 1-phenylethanol. Solvent-free conditions at 160C under different gas phases (oxygen, air, nitrogen and argon) were used. The thiazolium-based material displayed excellent performances. Further studies were carried out using unsupported thiazolium salts, with or without a methyl group at the C-2 position of the thiazolium moiety. These studies allowed us to propose a reaction me…
Heterogeneous Gold Catalyst: Synthesis, Characterization, and Application in 1,4-Addition of Boronic Acids to Enones
2015
The new 1 wt % Au/TiO2–UVM-7 catalyst was prepared and fully characterized. This heterogeneous catalyst proved to be active, selective and recyclable for the unprecedented gold-catalyzed 1,4-addition of various functionalized arylboronic acids to 2-cyclohexen-1-one and other selected enones using toluene as a solvent. The gold-based catalyst was recycled two times and played an active role in this reaction, and the nature of the solvent determined a remarkable change in the products’ selectivities.
Azoxybenzene rearrangement catalyzed by solid acids
2008
Abstract For the first time, the potential of acidic cation-exchange resin (sulfonated polystyrene) to catalyze the Wallach rearrangement of azoxybenzene into 4-hydroxyazobenzene has been proved. This finding reveals an alternative reaction path possible in a heterogeneous process using solid acids and may help to clear some doubts concerning the rearrangement mechanism postulated so far. The resin-induced reaction was found to proceed exclusively in a non-polar medium. Reasonable yield was obtained particularly in isooctane due to favorable distribution of azoxybenzene throughout the resin's matrix. On the contrary, the HY type zeolite did not activate the rearrangement, most probably beca…
First Principles Calculations for Hydrogenation of Acrolein on Pd and Pt: Chemoselectivity Depends on Steric Effects on the Surface
2016
The chemoselective hydrogenation of acrolein on Pt(111) and Pd(111) surfaces is investigated employing density functional theory calculations. The computed potential energy surfaces together with the analysis of reaction mechanisms demonstrate that steric effects are an important factor that governs chemoselectivity. The reactions at the C=O functionality require more space than the reactions at the C=C functionality. Therefore the formation of allyl alcohol is more favorable at low coverage, while the reduction of the C=C bond and the formation of propanal becomes kinetically more favorable at higher coverage. The elementary reaction steps are found to follow different reaction mechanisms,…
Hydrogenation of 2,4-Dinitro-toluene on Pd/C Catalysts: Computational Study on the Influence of the Molecular Adsorption Modes and of Steric Hindranc…
2002
Abstract A new time-dependent Monte Carlo algorithm was developed to simulate isobar and isotherm three-phase batch hydrogenation of 2,4-dinitro-toluene on Pd/C catalysts. A new reaction mechanism was formulated, involving 9 and 27 toluene derivatives, in solution and adsorbed on the surface, respectively. In fact, three different ways of adsorption were considered for all surface derivatives. Microscopic mechanistic hypotheses were formulated analyzing the mimicked surface populations able to reproduce the experimental catalytic activity–selectivity patterns at different times, temperatures, reagent concentrations, and catalyst particle morphologies. The three different adsorption modes, g…
Evidences of release and catch mechanism in the Heck reaction catalyzed by palladium immobilized on highly cross-linked-supported imidazolium salts
2014
Abstract Palladium (10 wt%) on a highly cross-linked imidazolium-based material was used as catalyst in 0.1 mol% in the Heck reaction between several alkenes and aryl iodides. Products were obtained from good to high yields. Deeper investigations showed a release of Pd species in solution and their capture by the imidazolium-based support. When a sixfold amount of support was employed the re-captured Pd species (0.5–0.6 wt%) were not anymore catalytically active. This result represents a new interesting aspect of this work since the highly cross-linked imidazolium-based material can act also as Pd scavenger avoiding the release of the metal in solution. Important differences between Heck an…
β-Amino alcohols from anilines and ethylene glycol through heterogeneous Borrowing Hydrogen reaction
2017
Abstract Borrowing Hydrogen (BH), also called Hydrogen Autotransfer (HA), reaction with neat ethylene glycol represents a key step in the preparation of β-amino alcohols. However, due to the stability of ethylene glycol, mono-activation has rarely been achieved. Herein, a combination of Pd/C and ZnO is reported as heterogeneous catalyst for this BH/HA reaction. This system results in an extremely air and moisture stable, and economic catalyst able to mono-functionalize ethylene glycol in water, without further activation of the diol. In this work, different diols and aromatic amines have been explored affording a new approach towards amino alcohols. This study reveals how the combination of…
Preface
2019
Preface of the book "Heterogeneous Photocatalysis Relationships with Heterogeneous Catalysis and Perspectives"
Kinetics of thiophene reactive adsorption on Ni/SiO2 and Ni/ZnO.
2008
Abstract Kinetics of thiophene reactive adsorption on Ni/SiO2 and Ni/ZnO was studied by thermal gravimetric analysis at 280–360 °C under 5–40 mbar of thiophene in H2. In the case of Ni/SiO2 the interaction proceeds in two steps: a rapid surface reaction is followed by a slower bulk transformation into Ni3S2. Maximum Ni conversion depends on reaction conditions and observed conversion profiles can be described by an exponential equation corresponding to a reaction of first order relatively to both sulfidable Ni amount and thiophene. The interaction between Ni/ZnO and thiophene proceeds in a rather different manner. A rapid increase of weight, similar to the first stage observed on Ni/SiO2, i…