The interaction of CO with a copper(ii) chloride oxy-chlorination catalyst

Guan, Shaoliang, Rossi, Giovanni E., Winfield, John M., Wilson, Claire, MacLaren, Donald, Morgan, David J. ORCID: https://orcid.org/0000-0002-6571-5731, Davies, Philip R. ORCID: https://orcid.org/0000-0003-4394-766X, Willock, David J. ORCID: https://orcid.org/0000-0002-8893-1090 and Lennon, David 2021. The interaction of CO with a copper(ii) chloride oxy-chlorination catalyst. Faraday Discussions 229 , pp. 318-340. 10.1039/D0FD00014K

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Abstract

The interaction of CO with an attapulgite-supported, KCl modified CuCl2 catalyst has previously been examined using a combination of XANES, EXAFS and DFT calculations. Exposing the catalyst to CO 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 stage, where the supported CuCl2 sample is exposed to a diluted stream of dichlorine; subsequent CO exposure at ∼643 K then leads to phosgene production. This communication describes a series of FTIR based micro-reactor measurements, coupled with characterisation measurements utilising TEM, XRD and XPS to define the nature of the catalyst at different stages of the reaction coordinate. The CuCl2 catalyst is able to support Deacon activity Image ID:d0fd00014k-t1.gif, establishing this work with the possibility of utilising the oxy-chlorination of CO to produce phosgene. Continuous dosing of CO at elevated temperatures over the chlorine pre-dosed CuCl2 catalyst shows diminishing phosgene production as a function of time-on-stream, indicating surface chlorine supply to be rate-limiting under the reaction conditions studied. A pictorial reaction scheme is proposed to account for the surface chemistry observed.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Additional Information:	This article is licensed under a Creative Commons Attribution 3.0 Unported Licence
Publisher:	Royal Society of Chemistry
ISSN:	1359-6640
Funders:	EPSRC
Date of First Compliant Deposit:	21 May 2021
Date of Acceptance:	10 February 2020
Last Modified:	03 May 2023 22:55
URI:	https://orca.cardiff.ac.uk/id/eprint/141502

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