4.8 Article

Nitrogen Modified Carbon Nano-Materials as Stable Catalysts for Phosgene Synthesis

Journal

ACS CATALYSIS
Volume 6, Issue 9, Pages 5843-5855

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.6b01424

Keywords

Cl-2 activation; transient COCl2 synthesis; N-containing carbon catalyst; electrophilic and nucleophilic carbon sites; in situ Raman spectroscopy; reaction mechanisms

Funding

  1. European Community [NMP-LA-2010-245988]

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The carbon-catalyzed reaction of Cl-2, and CO constitutes the most important industrial route to phosgene. Although defects in carbon lead to surface chemical reactions, direct polarization of C-heteroatom bonds induces a more successful Cl-2 catalytic activation, the rate-determining step in the overall catalytic cycle. The interplay between the electron donating and-withdrawing ability of the incorporated nitrogen substituents on the formation and stabilization of active sites was examined by X-ray photoelectron and Raman spectroscopy. Mechanistic studies indicate that the polarized Cl-2 induced by the direct interaction of Cl-2, with a strongly electron deficient carbon site in close proximity to a nitrogen substituent is essential for phosgene production. Nitrogen substitution into ordered carbon materials led to very active and stable carbon catalysts for COCl2 synthesis.

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