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Critical Role of Oxygen in Silver-Catalyzed Glaser-Hay Coupling on Ag(100) in Vacuum and in Solution on Ag Particles

Orozco, N, Kyriakou, G, Beaumont, SK, Fernandez Sanz, J, Holgado, JP, Taylor, MJ, Espinos, JP, Márquez, AM, Watson, DJ, Gonzalez-Elipe, AR and Lambert, R (2017) Critical Role of Oxygen in Silver-Catalyzed Glaser-Hay Coupling on Ag(100) in Vacuum and in Solution on Ag Particles Catalysis.

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Abstract

The essential role of oxygen in enabling heterogeneously catalyzed Glaser-Hay coupling of phenylacetylene on the Ag(100) was elucidated by STM, laboratory and synchrotron photoemission and DFT calculations. In the absence of co-adsorbed oxygen, phenylacetylene formed well-ordered dense overlayers which, with increasing temperature, desorbed without reaction. In striking contrast, even at 120 K, the presence of oxygen led to immediate and complete disruption of the organic layer due to abstraction of acetylenic hydrogen with formation of a disordered mixed layer containing immobile adsorbed phenylacetylide. At higher temperatures phenylacetylide underwent Glaser-Hay coupling to form highly ordered domains of diphenyldiacetylene that eventually desorbed without decomposition leaving the bare metal surface. DFT calculations showed that while acetylenic H abstraction was otherwise an endothermic process, oxygen adatoms triggered a reaction-initiating exothermic pathway leading to OH(a) + phenylacetylide, consistent with the experimental observations. Moreover, it was found that with a solution of phenylacetylene in nonane and in the presence of O2, Ag particles catalyzed Glaser-Hay coupling with high selectivity. Rigorous exclusion of oxygen from the reactor strongly suppressed the catalytic reaction. Interestingly, too much oxygen lowers the selectivity towards diphenyldiacetylene. Thus vacuum studies and theoretical calculations revealed the key role of oxygen in the reaction mechanism, subsequently borne out by catalytic studies with Ag particles that confirmed the presence of oxygen as a necessary and sufficient condition for the coupling reaction to occur. The direct relevance of model studies to mechanistic understanding of coupling reactions under conditions of practical catalysis was reaffirmed.

Item Type: Article
Subjects : Chemistry
Authors :
NameEmailORCID
Orozco, NUNSPECIFIEDUNSPECIFIED
Kyriakou, GUNSPECIFIEDUNSPECIFIED
Beaumont, SKUNSPECIFIEDUNSPECIFIED
Fernandez Sanz, JUNSPECIFIEDUNSPECIFIED
Holgado, JPUNSPECIFIEDUNSPECIFIED
Taylor, MJUNSPECIFIEDUNSPECIFIED
Espinos, JPUNSPECIFIEDUNSPECIFIED
Márquez, AMUNSPECIFIEDUNSPECIFIED
Watson, DJd.j.watson@surrey.ac.ukUNSPECIFIED
Gonzalez-Elipe, ARUNSPECIFIEDUNSPECIFIED
Lambert, RUNSPECIFIEDUNSPECIFIED
Date : 22 March 2017
Copyright Disclaimer : Copyright 2017 ACS
Uncontrolled Keywords : Glaser-Hay coupling, Silver surface, Catalysis, C-C bond formation, XPS, STM, DFT
Related URLs :
Depositing User : Symplectic Elements
Date Deposited : 17 May 2017 13:58
Last Modified : 18 May 2017 12:54
URI: http://epubs.surrey.ac.uk/id/eprint/841042

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