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

Guan, Shaoliang, Davies, Philip Rosser, Gibson, Emma K, Lennon, David, Rossi, Giovanni E., Winfield, John, Callison, June, Wells, Peter P. and Willock, David J 2018. Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene. Faraday Discussions 208 , pp. 67-85. 10.1039/C8FD00005K

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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 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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Advanced Research Computing @ Cardiff (ARCCA)
Cardiff Catalysis Institute (CCI)
Publisher: Royal Society of Chemistry
ISSN: 1359-6640
Funders: EPSRC, EPSRC
Date of First Compliant Deposit: 22 February 2018
Date of Acceptance: 16 January 2018
Last Modified: 28 Oct 2019 21:58
URI: http://orca.cf.ac.uk/id/eprint/109373

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