title: Identification of single-site gold catalysis in acetylene hydrochlorination.
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.
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.
authors.forename: Grazia
authors.identifier: 0000-0001-7562-6217
authors.initials: G
authors.lastname: Malta
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.
authors.forename: Simon A
authors.identifier: 0000-0003-4972-693X
authors.initials: SA
authors.lastname: Kondrat
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.
authors.forename: Simon J
authors.identifier: 0000-0002-6395-6646
authors.initials: SJ
authors.lastname: Freakley
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.
authors.forename: Catherine J
authors.identifier: 0000-0001-8953-6108
authors.initials: CJ
authors.lastname: Davies
authors.affiliation: Department of Materials Science and Engineering, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015, USA.
authors.forename: Li
authors.identifier: 0000-0001-9636-3014
authors.initials: L
authors.lastname: Lu
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.
authors.forename: Simon
authors.identifier: 0000-0001-8620-9574
authors.initials: S
authors.lastname: Dawson
authors.affiliation: UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory (RAL), Oxford OX11 0FA, UK.|Kathleen Lonsdale Building, Department of Chemistry, University College London, Gordon Street, London WC1H 0AJ, UK.
authors.forename: Adam
authors.identifier: 0000-0003-4671-6023
authors.initials: A
authors.lastname: Thetford
authors.affiliation: UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory (RAL), Oxford OX11 0FA, UK.|Kathleen Lonsdale Building, Department of Chemistry, University College London, Gordon Street, London WC1H 0AJ, UK.
authors.forename: Emma K
authors.identifier: 0000-0002-7839-3786
authors.initials: EK
authors.lastname: Gibson
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.
authors.forename: David J
authors.identifier: 0000-0002-6571-5731
authors.initials: DJ
authors.lastname: Morgan
authors.affiliation: UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory (RAL), Oxford OX11 0FA, UK.
authors.forename: Wilm
authors.identifier: 0000-0001-9208-8254
authors.initials: W
authors.lastname: Jones
authors.affiliation: UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory (RAL), Oxford OX11 0FA, UK.|Kathleen Lonsdale Building, Department of Chemistry, University College London, Gordon Street, London WC1H 0AJ, UK.|School of Chemistry, University of Southampton, Southampton SO17 1BJ, UK.|Diamond Light Source, Harwell Science and Innovation Campus, Chilton, Didcot OX11 0DE, UK.
authors.forename: Peter P
authors.identifier: 0000-0002-0859-9172
authors.initials: PP
authors.lastname: Wells
authors.affiliation: Process Technologies, Johnson Matthey PLC, Billingham TS23 1LB, UK.
authors.forename: Peter
authors.identifier: 0000-0002-9127-7907
authors.initials: P
authors.lastname: Johnston
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.|UK Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory (RAL), Oxford OX11 0FA, UK.|Kathleen Lonsdale Building, Department of Chemistry, University College London, Gordon Street, London WC1H 0AJ, UK.
authors.forename: C Richard A
authors.initials: CR
authors.lastname: Catlow
authors.affiliation: Department of Materials Science and Engineering, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015, USA.
authors.forename: Christopher J
authors.identifier: 0000-0001-5412-0970
authors.initials: CJ
authors.lastname: Kiely
authors.affiliation: Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK. hutch@cf.ac.uk.
authors.forename: Graham J
authors.identifier: 0000-0001-8885-1560
authors.initials: GJ
authors.lastname: Hutchings