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Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene
Authors:
Shaoliang
Guan
(Cardiff University; University of Glasgow)
,
Philip R.
Davies
(Cardiff University)
,
Emma K.
Gibson
(UK Catalysis Hub; Diamond Light Source; University College London)
,
David
Lennon
(University of Glasgow)
,
Giovanni E.
Rossi
(University of Glasgow)
,
John M.
Winfield
(University of Glasgow)
,
June
Callison
(UK Catalysis Hub)
,
Peter P.
Wells
(UK Catalysis Hub; Diamond Light Source; University of Southampton)
,
David J.
Willock
(Cardiff University)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Faraday Discussions
State:
Published (Approved)
Published:
February 2018
Diamond Proposal Number(s):
10306

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 370C 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.
Subject Areas:
Chemistry
Instruments:
B18-Core EXAFS
Documents:
C8FD00005K.pdf
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