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Volume 208, 2018
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Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene

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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 using 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.

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

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Publication details

The article was received on 15 Jan 2018, accepted on 16 Jan 2018 and first published on 20 Feb 2018


Article type: Paper
DOI: 10.1039/C8FD00005K
Citation: Faraday Discuss., 2018,208, 67-85
  • Open access: Creative Commons BY license
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    Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene

    S. Guan, P. R. Davies, E. K. Gibson, D. Lennon, G. E. Rossi, John M. Winfield, J. Callison, P. P. Wells and D. J. Willock, Faraday Discuss., 2018, 208, 67
    DOI: 10.1039/C8FD00005K

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