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)
|
Text
155440.pdf - Published Version Available under License Creative Commons Attribution. 1MB |
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 |
University Staff: Request a correction | Enlighten Editors: Update this record
Funder and Project Information
Funder and Project Information