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Deactivation of a single-site gold-on-carbon acetylene hydrochlorination catalyst: An X-ray absorption and inelastic neutron scattering study

Malta, Grazia, Kondrat, Simon A., Freakley, Simon J., Davies, Catherine, Dawson, Simon, Liu, Xi, Lu, Li, Dymkowski, Krzysztof, Fernandez-Alonso, F., Mukhopadhyay, Sanghamitra, Gibson, Emma Kate, Wells, Peter P., Parker, Stewart F., Kiely, Christopher J. and Hutchings, Graham J. 2018. Deactivation of a single-site gold-on-carbon acetylene hydrochlorination catalyst: An X-ray absorption and inelastic neutron scattering study. ACS Catalysis 8 (9) , pp. 8493-8505. 10.1021/acscatal.8b02232

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Abstract

Single-site Au species supported on carbon have been shown to be the active sites for acetylene hydrochlorination. The evolution of these single-site species has been monitored by Au L3 X-ray Absorption Spectroscopy (XAS). Alternating between a standard reaction mixture of HCl/C2H2 and the single reactants, has provided insights into the reaction mechanism and catalyst deactivation processes. We demonstrate that oxidative addition of HCl across an Au(I) chloride species requires concerted addition with C2H2, in accordance with both the XAS measurements of Au oxidation state and the reaction kinetics being 1st order with respect to each reactant. The addition of excess C2H2 changes the Au speciation and results in the formation of oligomeric acetylene species which were detected by inelastic neutron scattering. Catalyst deactivation at extended reaction times can be correlated with the formation of metallic Au particles. The presence of this Au(0) species generated during the sequential gas experiments or after prolonged reaction times, results in the analysis of the normalised near edge white line intensity of the Au L3 X-ray absorption spectrum alone becoming an unsuitable guide for identifying the active Au species, affecting the strong correlation between normalized white line height and VCM productivity usually observed in the active catalyst. Thus, a combination of scanning transmission electron microscopy and detailed modelling of whole XAS spectrum was required to distinguish active Au(I) and Au(III) species from the spectator Au(0) component.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Cardiff Catalysis Institute (CCI)
Chemistry
Publisher: American Chemical Society
ISSN: 2155-5435
Funders: Engineering and Physical Sciences Research Council
Date of First Compliant Deposit: 31 July 2018
Date of Acceptance: 27 July 2018
Last Modified: 27 Jun 2019 08:28
URI: http://orca.cf.ac.uk/id/eprint/113809

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