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

Guan, S., Davies, P. R., Gibson, E. K., Lennon, D. , Rossi, G. E., Winfield, J. M., Callison, J., Wells, P. P. and Willock, D. J. (2018) Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene. Faraday Discussions, 208, pp. 67-85. (doi: 10.1039/C8FD00005K) (PMID:29850700)

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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:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Winfield, Professor John and Guan, Mr Shaoliang and Rossi, Giovanni and Lennon, Professor David
Authors: Guan, S., Davies, P. R., Gibson, E. K., Lennon, D., Rossi, G. E., Winfield, J. M., Callison, J., Wells, P. P., and Willock, D. J.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Faraday Discussions
Publisher:Royal Society of Chemistry
ISSN:1359-6640
ISSN (Online):1364-5498
Published Online:20 February 2018
Copyright Holders:Copyright © 2018 The Authors
First Published:First published in Faraday Discussions 208:67-85
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
557001Catalytic Science in the Harwell Research CentreDavid LennonEngineering and Physical Sciences Research Council (EPSRC)EP/I019693/1CHEM - CHEMISTRY
654181Catalytic HDO (UK Catalysis hub)Samuel JacksonEngineering and Physical Sciences Research Council (EPSRC)EP/K014706/1CHEM - CHEMISTRY
652891Towards closing the chlorine cycle in large-scale chemical manufacturing processes (UK Catalysis hub)David LennonEngineering and Physical Sciences Research Council (EPSRC)EP/K014854/1CHEM - CHEMISTRY