Identification of single-site gold catalysis in acetylene hydrochlorination

Grazia Malta; Simon A Kondrat; Simon J Freakley; Catherine J Davies; Li Lu; Simon Dawson; Adam Thetford; Emma K Gibson; David J Morgan; Wilm Jones; Peter P Wells; Peter Johnston; C Richard A Catlow; Christopher J Kiely; Graham J Hutchings

doi:10.1126/science.aal3439

Identification of single-site gold catalysis in acetylene hydrochlorination

Science. 2017 Mar 31;355(6332):1399-1403. doi: 10.1126/science.aal3439.

Authors

Grazia Malta¹, Simon A Kondrat¹, Simon J Freakley¹, Catherine J Davies¹, Li Lu², Simon Dawson¹, Adam Thetford^{3

4}, Emma K Gibson^{3

4}, David J Morgan¹, Wilm Jones³, Peter P Wells^{3

4

5

6}, Peter Johnston⁷, C Richard A Catlow^{1

3

4}, Christopher J Kiely², Graham J Hutchings⁸

Affiliations

¹ Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.
² Department of Materials Science and Engineering, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015, USA.
³ UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory (RAL), Oxford OX11 0FA, UK.
⁴ Kathleen Lonsdale Building, Department of Chemistry, University College London, Gordon Street, London WC1H 0AJ, UK.
⁵ School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK.
⁶ Diamond Light Source, Harwell Science and Innovation Campus, Chilton, Didcot OX11 0DE, UK.
⁷ Process Technologies, Johnson Matthey PLC, Billingham TS23 1LB, UK.
⁸ Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK. [email protected].

PMID: 28360324
DOI: 10.1126/science.aal3439

Abstract

There remains considerable debate over the active form of gold under operating conditions of a recently validated gold catalyst for acetylene hydrochlorination. We have performed an in situ x-ray absorption fine structure study of gold/carbon (Au/C) catalysts under acetylene hydrochlorination reaction conditions and show that highly active catalysts comprise single-site cationic Au entities whose activity correlates with the ratio of Au(I):Au(III) present. We demonstrate that these Au/C catalysts are supported analogs of single-site homogeneous Au catalysts and propose a mechanism, supported by computational modeling, based on a redox couple of Au(I)-Au(III) species.

Publication types

Research Support, Non-U.S. Gov't