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

Guan, Shaoliang, Davies, Philip Rosser ORCID: https://orcid.org/0000-0003-4394-766X, Gibson, Emma K, Lennon, David, Rossi, Giovanni E., Winfield, John, Callison, June, Wells, Peter P. and Willock, David J ORCID: https://orcid.org/0000-0002-8893-1090 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:	20 Sep 2024 16:44
URI:	https://orca.cardiff.ac.uk/id/eprint/109373

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