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

Guan, S., Rossi, G., Winfield, J., Wilson, C. , MacLaren, D. , Morgan, D., Davies, P., Willock, D. and Lennon, D. (2021) The interaction of CO with a copper(II) chloride oxy-chlorination catalyst. Faraday Discussions, 229, pp. 318-340. (doi: 10.1039/D0FD00014K) (PMID:33644789)

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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 (2HCl + ½ O2  Cl2 + H2O), establishing this work with the possibility of utilising the oxy-chlorination of CO to produce phosgene. However, 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:Articles
Additional Information:The resources and support provided by the UK Catalysis Hub via membership of the UK Catalysis Hub consortium and funded by EPSRC (grants EP/K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1 and EP/M013219/1) are gratefully acknowledged. Ineos Chlor Ltd. is thanked for provision of the catalyst. XPS data collection was performed at the EPSRC National Facility for XPS (“HarwellXPS”) under contract number PR16195. Colin How (School of Physics and Astronomy, University of Glasgow) is thanked for technical support for the TEM measurements. Dr James Campbell (School of Chemistry, University of Glasgow) is thanked for assistance with the DRIFTS measurements.
Glasgow Author(s) Enlighten ID:Winfield, Professor John and MacLaren, Dr Donald and Guan, Mr Shaoliang and Wilson, Dr Claire and Rossi, Giovanni and Lennon, Professor David
Authors: Guan, S., Rossi, G., Winfield, J., Wilson, C., MacLaren, D., Morgan, D., Davies, P., Willock, D., and Lennon, D.
College/School:College of Science and Engineering > School of Chemistry
College of Science and Engineering > School of Physics and Astronomy
Journal Name:Faraday Discussions
Publisher:Royal Society of Chemistry
ISSN (Online):1364-5498
Published Online:11 February 2020
Copyright Holders:Copyright © Royal Society of Chemistry 2020
First Published:First published in Faraday Discussions 229:318-340
Publisher Policy:Reproduced under a Creative Commons license

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
169321Catalytic HDO : Queen's University of Belfast ref R1188CCESamuel JacksonEngineering and Physical Sciences Research Council (EPSRC)EP/K014706/1Chemistry