Temperature-induced ordering of metal/adsorbate structures at electrochemical interfaces

Christopher A Lucas; Paul Thompson; Michael Cormack; Alexander Brownrigg; Ben Fowler; Dusan Strmcnik; Vojislav Stamenkovic; Jeff Greeley; Andreas Menzel; Hoydoo You; Nenad M Marković

doi:10.1021/ja9014666

Temperature-induced ordering of metal/adsorbate structures at electrochemical interfaces

J Am Chem Soc. 2009 Jun 10;131(22):7654-61. doi: 10.1021/ja9014666.

Authors

Christopher A Lucas¹, Paul Thompson, Michael Cormack, Alexander Brownrigg, Ben Fowler, Dusan Strmcnik, Vojislav Stamenkovic, Jeff Greeley, Andreas Menzel, Hoydoo You, Nenad M Marković

Affiliation

¹ Oliver Lodge Laboratory, Department of Physics, University of Liverpool, Liverpool, L69 7ZE, United Kingdom. clucas@liv.ac.uk

PMID: 19489644
DOI: 10.1021/ja9014666

Abstract

The influence of temperature changes in water-based electrolytes on the atomic structure at the electrochemical interface has been studied using in situ surface X-ray scattering (SXS) in combination with cyclic voltammetry. Results are presented for the potential-dependent surface reconstruction of Au(100), the adsorption and ordering of bromide anions on the Au(100) surface, and the adsorption and oxidation of CO on Pt(111) in pure HClO(4) and in the presence of anions. These systems represent a range of structural phenomena, namely metal surface restructuring and ordering transitions in both nonreactive spectator species and reactive adsorbate layers. The key effect of temperature appears to be in controlling the kinetics of the surface reactions that involve oxygenated species, such as hydroxyl adsorption and oxide formation. The results indicate that temperature effects should be considered in the determination of structure-function relationships in many important electrochemical systems.