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Controlling the speciation and reactivity of carbon-supported gold nanostructures for catalysed acetylene hydrochlorination.
Journal article

Controlling the speciation and reactivity of carbon-supported gold nanostructures for catalysed acetylene hydrochlorination.

  • Kaiser SK Institute for Chemical and Bioengineering , Department of Chemistry and Applied Biosciences , ETH Zurich , Vladimir-Prelog-Weg 1 , 8093 Zurich , Switzerland . Email: jpr@chem.ethz.ch.
  • Lin R Institute for Chemical and Bioengineering , Department of Chemistry and Applied Biosciences , ETH Zurich , Vladimir-Prelog-Weg 1 , 8093 Zurich , Switzerland . Email: jpr@chem.ethz.ch.
  • Mitchell S Institute for Chemical and Bioengineering , Department of Chemistry and Applied Biosciences , ETH Zurich , Vladimir-Prelog-Weg 1 , 8093 Zurich , Switzerland . Email: jpr@chem.ethz.ch.
  • Fako E Institute of Chemical Research of Catalonia (ICIQ) , The Barcelona Institute of Science and Technology , Av. Països Catalans 16 , 43007 Tarragona , Spain.
  • Krumeich F Institute for Chemical and Bioengineering , Department of Chemistry and Applied Biosciences , ETH Zurich , Vladimir-Prelog-Weg 1 , 8093 Zurich , Switzerland . Email: jpr@chem.ethz.ch.
  • Hauert R Swiss Federal Laboratories for Materials Science and Technology , EMPA , Überlandstrasse 129 , 8600 Dübendorf , Switzerland.
  • Safonova OV Paul Scherrer Institut , 5232 Villigen PSI , Switzerland.
  • Kondratenko VA Leibniz-Institut für Katalyse e. V. , Albert-Einstein-Straße 29a , 18059 Rostock , Germany.
  • Kondratenko EV Leibniz-Institut für Katalyse e. V. , Albert-Einstein-Straße 29a , 18059 Rostock , Germany.
  • Collins SM Department of Materials Science and Metallurgy , University of Cambridge , 27 Charles Babbage Road , Cambridge CB3 0FS , UK.
  • Midgley PA Department of Materials Science and Metallurgy , University of Cambridge , 27 Charles Babbage Road , Cambridge CB3 0FS , UK.
  • López N Institute of Chemical Research of Catalonia (ICIQ) , The Barcelona Institute of Science and Technology , Av. Països Catalans 16 , 43007 Tarragona , Spain.
  • Pérez-Ramírez J Institute for Chemical and Bioengineering , Department of Chemistry and Applied Biosciences , ETH Zurich , Vladimir-Prelog-Weg 1 , 8093 Zurich , Switzerland . Email: jpr@chem.ethz.ch.
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  • 2019-02-13
Published in:
  • Chemical science. - 2019
General Chemistry
English Carbon-supported gold catalysts have the potential to replace the toxic mercuric chloride-based system applied industrially for acetylene hydrochlorination, a key technology for the manufacture of polyvinyl chloride. However, the design of an optimal catalyst is essentially hindered by the difficulties in assessing the nature of the active site. Herein, we present a platform of carbon supported gold nanostructures at a fixed metal loading, ranging from single atoms of tunable oxidation state and coordination to metallic nanoparticles, by varying the structure of functionalised carbons and use of thermal activation. While on activated carbon particle aggregation occurs progressively above 473 K, on nitrogen-doped carbon gold single atoms exhibit outstanding stability up to temperatures of 1073 K and under reaction conditions. By combining steady-state experiments, density functional theory, and transient mechanistic studies, we assess the relation between the metal speciation, electronic properties, and catalytic activity. The results indicate that the activity of gold-based catalysts correlates with the population of Au(i)Cl single atoms and the reaction follows a Langmuir-Hinshelwood mechanism. Strong interaction with HCl and thermodynamically favoured acetylene activation were identified as the key features of the Au(i)Cl sites that endow their superior catalytic performance in comparison to N-stabilised Au(iii) counterparts and gold nanoparticles. Finally, we show that the carrier (activated carbon versus nitrogen-doped carbon) does not affect the catalytic response, but determines the deactivation mechanism (gold particle aggregation and pore blockage, respectively), which opens up different options for the development of stable, high-performance hydrochlorination catalysts.
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  • English
Open access status
gold
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https://sonar.ch/global/documents/119279
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