Study of the isomerization of 13C labelled methylpentanes on oxygen modified bulk tungsten carbides

Literature Information

Publication Date 2000-06-09
DOI 10.1039/B000635L
Impact Factor 3.676
Authors

V. Keller, F. Garin, G. Maire


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Abstract

The reactions of labelled 2- and 3-methylpentanes were carried out on three different oxygen modified bulk tungsten carbides varying by their oxygen treatment temperature. In all cases, isomerization took place ia bond shift mechanisms; no cyclic mechanism was involved in contrast to metals like Pt, Pd or Ir where such mechanism occurs. Alkoxy and σ-alkyl intermediates were put forward as adsorbed species responsible for isomerization for bulk tungsten carbides treated by O2 at moderate temperature (350°C) over a short period of time (5 min) and at high temperature (700°C) for 4 h, respectively. These intermediate species are respectively correlated to an acidic and a metallic behavior of the catalytic surfaces. The increase of the O2 treatment time at 350°C results in the presence of both kinds of these mechanisms for isomerization, a bifunctional behavior takes place where metallic and acidic characters are present. To explain the presence of terminal-13C on acidic catalysts, a “protonated cyclopropane alkoxy species” intermediate responsible for isomerization was proposed. The driving force for the formation of such species being the presence of stable alkoxy species, general reaction pathways are discussed for the different kinds of catalysts.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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