Volume 208, 2018

Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene

Abstract

The interaction of CO with an attapulgite-supported Cu(II)Cl2 catalyst has been examined in a micro-reactor arrangement. CO exposure to the dried, as-received catalyst at elevated temperatures leads to the formation of CO2 as the only identifiable product. However, phosgene production can be induced by using a catalyst pre-treatment where the supported Cu(II)Cl2 sample is exposed to a diluted stream of chlorine. Subsequent CO exposure at ∼370 °C then leads to phosgene production. In order to investigate the origins of this atypical set of reaction characteristics, a series of X-ray absorption experiments were performed that were supplemented by DFT calculations. XANES measurements establish that at the elevated temperatures connected with phosgene formation, the catalyst is comprised of Cu+ and a small amount of Cu2+. Moreover, the data show that unique to the chlorine pre-treated sample, CO exposure at elevated temperature results in a short-lived oxidation of the copper. On the basis of calculated CO adsorption energies, DFT calculations indicate that a mixed Cu+/Cu2+ catalyst is required to support CO chemisorption.

Graphical abstract: Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
15 Jan 2018
Accepted
16 Jan 2018
First published
20 Feb 2018
This article is Open Access
Creative Commons BY license

Faraday Discuss., 2018,208, 67-85

Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene

S. Guan, P. R. Davies, E. K. Gibson, D. Lennon, G. E. Rossi, John M. Winfield, J. Callison, P. P. Wells and D. J. Willock, Faraday Discuss., 2018, 208, 67 DOI: 10.1039/C8FD00005K

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