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

Grazia Malta, Simon A Kondrat, Simon J Freakley, Catherine J Davies, Simon Dawson, Xi Liu, Li Lu, Krzysztof Dymkowski, F Fernandez-Alonso, Sanghamitra Mukhopadhyay

Research output: Contribution to journalArticle

12 Citations (Scopus)

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 first order with respect to each reactant. 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. These Au(0) species generated during the sequential gas experiments, or after prolonged reaction times, results in the analysis of the normalized near-edge white line intensity 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 modeling of whole XAS spectrum was required to distinguish active Au(I) and Au(III) species from the spectator Au(0) component.
Original languageEnglish
Pages (from-to)8493-8505
Number of pages13
JournalACS Catalysis
Volume8
Issue number9
Early online date27 Jul 2018
DOIs
Publication statusPublished - 7 Sep 2018

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

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 J; Dawson, Simon; Liu, Xi; Lu, Li; Dymkowski, Krzysztof; Fernandez-Alonso, F; Mukhopadhyay, Sanghamitra.

In: ACS Catalysis, Vol. 8, No. 9, 07.09.2018, p. 8493-8505.

Research output: Contribution to journalArticle

Malta, G, Kondrat, SA, Freakley, SJ, Davies, CJ, Dawson, S, Liu, X, Lu, L, Dymkowski, K, Fernandez-Alonso, F & Mukhopadhyay, S 2018, 'Deactivation of a single-site gold-on-carbon acetylene hydrochlorination catalyst: An X-ray absorption and inelastic neutron scattering study', ACS Catalysis, vol. 8, no. 9, pp. 8493-8505. https://doi.org/10.1021/acscatal.8b02232
Malta, Grazia ; Kondrat, Simon A ; Freakley, Simon J ; Davies, Catherine J ; Dawson, Simon ; Liu, Xi ; Lu, Li ; Dymkowski, Krzysztof ; Fernandez-Alonso, F ; Mukhopadhyay, Sanghamitra. / Deactivation of a single-site gold-on-carbon acetylene hydrochlorination catalyst: An X-ray absorption and inelastic neutron scattering study. In: ACS Catalysis. 2018 ; Vol. 8, No. 9. pp. 8493-8505.
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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 first order with respect to each reactant. 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. These Au(0) species generated during the sequential gas experiments, or after prolonged reaction times, results in the analysis of the normalized near-edge white line intensity 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 modeling of whole XAS spectrum was required to distinguish active Au(I) and Au(III) species from the spectator Au(0) component.",
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