Surface State Trapping and Mobility Revealed by Junction Electrochemistry of Nano-Cr2O3

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doi:10.1071/CH11382

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Affiliated with RACI

Royal Australian
Chemical Institute

Surface State Trapping and Mobility Revealed by Junction Electrochemistry of Nano-Cr₂O₃

Charles Y. Cummings ^A , Gary A. Attard ^B , John M. Mitchels ^A and Frank Marken ^A ^C

^A Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK.
^B Cardiff University, School of Chemistry, Cardiff Catalysis Institute, Cardiff CF10 3AT, UK.
^C Corresponding author. Email: f.marken@bath.ac.uk

Australian Journal of Chemistry 65(1) 65-71 http://dx.doi.org/10.1071/CH11382
Submitted: 2 October 2011 Accepted: 14 November 2011 Published: 15 December 2011





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Abstract

Hydrous chromium oxide nanoparticles (~15 nm diameter) are assembled from a colloidal solution onto tin-doped indium oxide (ITO) substrates by layer-by-layer electrostatic deposition with aqueous carboxymethyl-cellulose sodium salt binder. Calcination produces purely inorganic mesoporous films (average thickness increase per layer of 1 nm) of chromia Cr₂O₃. When immersed in aqueous carbonate buffer at pH 10 and investigated by cyclic voltammetry, a chemically reversible oxidation is observed because of a conductive layer at the chromia surface (formed during initial potential cycling). This is attributed to a surface Cr^III/IV process. At more positive potentials higher oxidation states are accessible before film dissolution. The effects of film thickness and pH on voltammetric responses are studied. X-Ray photoelectron spectroscopy (XPS) evidence for higher chromium oxidation states is obtained. ITO junction experiments are employed to reveal surface conduction by Cr^III/IV and Cr^IV/V ‘mobile surface states’ and an estimate is obtained for the apparent Cr^III/IV charge surface diffusion coefficient D_app = 10^–13 m² s^–1. The junction experiment distinguishes mobile surface redox sites from energetically distinct deeper-sitting ‘trapped states’.

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