Constante catalytique

Résumé

En enzymologie, la constante catalytique, notée kcat, également appelée turnover number (TON, parfois francisé en « nombre de rotations »), représente le nombre maximum de molécules de substrat transformées par seconde et par molécule d'enzyme. Elle peut être déduite de la vitesse maximale de réaction Vmax et de la concentration en sites catalytiques [E]T par la relation : :k_\mathrm{cat} = \frac{V_\max}{[E]_\mathrm{T}}. Par exemple, l'anhydrase carbonique, l'une des enzymes les plus rapides connues, a une constante catalytique de , voire , ce qui signifie que chaque molécule d'anhydrase carbonique peut, selon les conditions, produire jusqu'à un million d'ions bicarbonate par seconde. Le mot turnover number a une signification différente quand il est employé dans le domaine de la catalyse: il correspond alors au nombre de moles de substrat qu'une mole de catalyseur peut transformer avant de s'inactiver. Un catalyseur qui ne s'inactive pas aurait un "turnover number" inf

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https://fr.wikipedia.org/wiki/Constante_catalytique

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Transition-metal-catalyzed hydrosilylation of olefins is one of the most important methods for the preparation of organosilicon compounds, which have broad applications in both synthetic and material chemistry. For decades, precious metals, principally platinum-based complexes, have been utilized as catalysts for olefin hydrosilylation. However, due to the high and volatile cost and low abundance of Pt, the development of active and selective catalysts based on Earth-abundant metals is highly desirable. In the first chapter, a short overview of state-of-the-art Pt catalysts and recent advances in development of Fe, Co and Ni-catalysts for olefin hydrosilylation is given. The applications, mechanisms and remaining challenges of transition-metal-catalyzed hydrosilylation are discussed. In the chapter 2, chemoselective anti-Markovnikov hydrosilylation of functionalized alkenes using well-defined bis(amino)amide nickel pincer complexes is described. The catalysts exhibit both high turnover frequencies and turnover numbers. Alkenes containing amino, ester, amido, ketone, and formyl groups are selectively hydrosilylated with Ph2SiH2. Chemoselective hydrosilylation of carbon-carbon double bond in the presence of formyl group using a base metal catalyst is reported for the first time. A modification of reaction conditions allows tandem isomerization-hydrosilylation reactions of internal alkenes to give terminal alkyl silanes. Hydrosilylation of alkenes with tertiary silanes is more attractive from practical point of view. The screening of various nickel alkoxide complexes with reduced steric bulk led us to discovery of an efficient heterogeneous catalyst for alkene hydrosilylation with commercially relevant tertiary silanes (chapter 3). The catalyst exhibits high activity in anti-Markovnikov hydrosilylation of unactivated terminal alkenes and isomerizing hydrosilylation of internal alkenes. The catalyst can be applied to synthesize a single terminal alkyl silane from a mixture of internal and terminal alkene isomers. Furthermore, the same catalyst can be used to remotely functionalize an internal alkene derived from a fatty acid. Chapter 4 describes a catalytic system composed of a nickel amido(bisoxazoline) complex and NaOtBu for an unexpected synthetic transformation, leading to the synthesis of functionalized alkyl hydrosilanes from readily available alkenes and alkoxysilanes. This method provides a convenient and safe alternative to hydrosilylation using flammmable and potentially dangerous Me2SiH2, MeSiH3 and SiH4. The reaction mechanism was also described. Efficient and atom-economical creation of C-N bond is one of the major tasks in synthetic organic chemistry. Direct C-H amination has emerged as an attractive method for the construction of new C-N bonds. In the chapter 5 a new transition-metal free method for the intermolecular amination of the alpha-C-H bonds of ethers is described. Using a hypervalent iodine reagent as oxidant the amination of cyclic and acyclic alkyl ethers with a wide range of amides, imides, and amines was achieved. The utility of this method was demonstrated in the synthesis of Tegafur and its analogues. This transition-metal-free method provides a rapid access to a large number of nitrogen-containing organic molecules that may serve as useful synthetic intermediates or biologically active agents.

EPFL2016

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Supported ruthenium nanoparticles for supercritical water gasification - synthesis, activity and stability

Christopher Marc Hunston

Supercritical water gasification (SCWG) is a promising and versatile technology for the conversion of a variety of wet biomass streams into renewable natural gas. In this work, the focus was set on methane production with the help of an active and stable methanation catalyst. The supercritical water (SCW) environment can lead to rapid catalyst deactivation through different mechanisms, namely poisoning, coking, sintering or leaching. Although addressed, it remains challenging to disentangle them in SCWG. The goal of this thesis is to get a better understanding of the aforementioned deactivations pathways by trying to study them individually, in order to tailor an active and robust SCWG catalyst.The intrinsic gasification activity of carbon supports exhibiting different properties was assessed by feeding glycerol at 400°C and 30MPa. The negative effect of micropores was shown by significant coke deposition and surface area loss around 90%, compared to mesoporous carbons that only lost 20%. Carbon nanofibers (CNF) proved to be an interesting support showing very good stability and inertness. The synthesis of 5%Ru catalysts on selected supports confirmed these trends. Highly microporous Ru/C catalysts were less stable than the ones supported on carbon frameworks of more open pore structure. Ru/CNF seemed to be a promising SCWG catalyst, with an enhanced resistance towards coke formation. The completely open pore structure of CNF was found to be a crucial parameter.Ruthenium loss was investigated by measuring the its content in the process waters with ICP-MS. Ru was successfully quantified at levels close to thermodynamic models for Ru/AC and Ru/CNF of different loadings (0.01-0.2 µg L-1). Furthermore, the process parameters had no effect on the quantified Ru, showing that the steady-state loss represents a thermodynamically-driven leaching. Fluctuations in feed rate and pressure damaged the catalyst through friction and led higher Ru losses, mainly through the release of carbon domains containing Ru. Metal oxides were compared to AC by synthesising 2%Ru catalysts on alpha-Al2O3, ZrO2 and TiO2. They yielded 20-40 times higher Ru loss rates than for 2%Ru/AC and a significantly lower activity, confirming once again the superiority of Ru/C as SCWG catalyst. Ru losses were similar on larger rigs during glycerol and sewage sludge gasification, with values around 0.14-0.29 µg gRu-1 h-1.With Ru/CNF proving to be an interesting SCWG catalyst, more in-depth studies were performed on this system. Catalysts of different loadings (1-30%) were successfullysynthesised yielding very small Ru NPs (0.9-2.2 nm) with an easy synthesis method. Ru/CNF catalysts exhibited high gasification activities and improved stability compared to Ru/AC. The initial activity correlated with the Ru dispersion. However, 1%Ru/CNF catalysts underwent rapid deactivation compared to 5%Ru/CNF, showing the importance of site density to avoid rapid deactivation. The effect of surface Ru atom density was shown with a optimum in turnover frequency in the range 0.4-0.7 atomRu,sfc nm-2. For the first time, a particle size effect and more importantly a surface atom density effect was shown during SCWG of glycerol. Coke deposition was also investigated and observed at very high space velocities. The coke deposits could partially be removed by extraction in a mix of solvents, opening a potential new route for the regeneration of Ru/C catalysts.

EPFL2021

Chargement

Chemoselective Alkene Hydrosilylation Catalyzed by Nickel Pincer Complexes

Jeanne Marine Edith Becouse, Ivan Buslov, Xile Hu, Simona Mazza, Mickael Montandon-Clerc

Chemoselective hydrosilylation of functionalized alkenes is difficult to achieve using base-metal catalysts. Reported herein is that well-defined bis(amino) amide nickel pincer complexes are efficient catalysts for anti-Markovnikov hydrosilylation of terminal alkenes with turnover frequencies of up to 83000 per hour and turnover numbers of up to 10000. Alkenes containing amino, ester, amido, ketone, and formyl groups are selectively hydrosilylated. A slight modification of reaction conditions allows tandem isomerization/hydrosilylation reactions of internal alkenes using these nickel catalysts.

Wiley-Blackwell2015

Chargement

Supported ruthenium nanoparticles for supercritical water gasification - synthesis, activity and stability

Christopher Marc Hunston

EPFL2021

EPFL2016