Journal ArticleDOI
The role of the solvent in TS-1 chemistry: active or passive? An early study revisited
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TLDR
In this article, a mechanistic pathway for the hydroxylation of paraffinic and aromatic C-H bonds is suggested, and a dual function is postulated for the solvent in relation to its effects on kinetics.Abstract:
The oxidation of n-hexane with hydrogen peroxide, catalyzed by TS-1 in various solvents, is reported. The initial rate of reaction decreases in the order: t-butanol > t-butanol/water > methanol ≈ acetonitrile ≈ water, whereas the reverse trend was observed for the adsorption of n-hexane in the catalyst. A dual function is postulated for the solvent in relation to its effects on kinetics. It assists the sorption/desorption of reagents/products in TS-1 (passive role) and participates in the catalytic cycle, through interactions with polar species involved in it (active role). A mechanistic pathway for the hydroxylation of paraffinic and aromatic C–H bonds is suggested.read more
Citations
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Lewis acids as catalysts in oxidation reactions: from homogeneous to heterogeneous systems.
TL;DR: This review is focused on the use of solid Lewis acids to promote catalytic oxidations, and the core of the review is organized to show the evolution from the simplest strategy for heterogeneizing homogeneous catalysts, to the more elaborate ones in which the active sites are part of the solid structure.
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Reactivity of Surface Species in Heterogeneous Catalysts Probed by In Situ X-ray Absorption Techniques
TL;DR: (Article begins on next page)
Journal ArticleDOI
Reactivity of Ti(IV) species hosted in TS-1 towards H2O2–H2O solutions investigated by ab initio cluster and periodic approaches combined with experimental XANES and EXAFS data: a review and new highlights
TL;DR: How the most-advanced experimental and theoretical physical chemistry tools must be used synergistically to understand the reactivity of Ti-silicalite-1 (TS-1) in an important number of low-temperature oxidation reactions with aqueous H( 2)O(2) as the oxidant is underline.
Journal ArticleDOI
Chemical and Technical Aspects of Propene Oxide Production via Hydrogen Peroxide (HPPO Process)
TL;DR: In this article, the state of the art of the scientific knowledge and technical aspects related to propene oxide synthesis in the presence of TS-1 catalyst have been reviewed and compared.
Journal ArticleDOI
Photochemical and FT-IR probing of the active site of hydrogen peroxide in Ti silicalite sieve.
Wenyong Lin,Heinz Frei +1 more
TL;DR: The TiOOH moiety was shown by in situ FT-IR monitoring to oxidize small olefins at room temperature in the dark (propylene) or under photoexcitation of the LMCT chromophore (ethylene), the first direct detection of the active oxidation site in H(2)O(2)-loaded Ti silicalite sieve.
References
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Journal ArticleDOI
Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage
Journal ArticleDOI
Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalite
TL;DR: In this article, the epoxidation of propylene with hydrogen peroxide in the liquid phase, in the presence of titanium silicalite catalyst (TS-1), is described.
Journal ArticleDOI
Epoxidation of Lower Olefins with Hydrogen Peroxide and Titanium Silicalite
M. G. Clerici,P. Ingallina +1 more
TL;DR: In this article, the epoxidation of lower olefins, catalysed by titanium silicalite (TS-1) under mild conditions, is reported. But the reaction may be performed at near room temperature, in dilute alcoholic or aqueous solutions of hydrogen peroxide.
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Vanadium(V) peroxy complexes. New versatile biomimetic reagents for epoxidation of olefins and hydroxylation of alkanes and aromatic hydrocarbons
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Oxyfunctionalization of alkanes with hydrogen peroxide on titanium silicalite
TL;DR: In this paper, it was shown that titanium silicalite, a microporous crystalline Ti-silica, is able to activate secondary and tertiary carbon atoms in alkanes, so that they may be oxidized to alcohols and subsequently to ketones using aqueous H2O2.
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Epoxidation of Lower Olefins with Hydrogen Peroxide and Titanium Silicalite
M. G. Clerici,P. Ingallina +1 more