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Catalytic Hydrogen-Chlorine Exchange between Chlorinated Hydrocarbons under Oxygen-Free Conditions

Authors

  • Alwies W. A. M. van der Heijden,

    1. Inorganic Chemistry and Catalysis Group, Department of Chemistry, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht (The Netherlands), Fax: (31) 30-251-1027
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  • Simon G. Podkolzin Dr.,

    1. The Dow Chemical Company, Core Research and Development, Midland, Michigan 48674 (USA)
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  • Mark E. Jones Dr.,

    1. The Dow Chemical Company, Core Research and Development, Midland, Michigan 48674 (USA)
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  • Johannes H. Bitter Dr.,

    1. Inorganic Chemistry and Catalysis Group, Department of Chemistry, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht (The Netherlands), Fax: (31) 30-251-1027
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  • Bert M. Weckhuysen Prof. Dr. ir.

    1. Inorganic Chemistry and Catalysis Group, Department of Chemistry, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht (The Netherlands), Fax: (31) 30-251-1027
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  • The authors thank NWO-CW VICI for financial support. The metathesis reaction between CCl4 and CH2Cl2 was discovered by Mark E. Jones at the Dow Chemical Company. The carbon nanofibers were synthesized by Arjan J. Plomp.

Abstract

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Pass the parcel: Activity experiments show that LaCl3 supported on carbon nanofibers is a highly active, selective, and stable catalyst for the H–Cl exchange reaction between CCl4 and CH2Cl2 to form CHCl3 (see scheme) in the absence of either lattice or gas-phase oxygen. Density functional calculations suggest that the reaction proceeds through the formation of weakly adsorbed Cl and H species which can be exchanged between the reactants.

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