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
+ Author Affiliations
- Author Affiliations
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 https://doi.org/10.1071/CH11382
Submitted: 2 October 2011 Accepted: 14 November 2011 Published: 15 December 2011
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 CrIII/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 CrIII/IV and CrIV/V ‘mobile surface states’ and an estimate is obtained for the apparent CrIII/IV charge surface diffusion coefficient Dapp = 10–13 m2 s–1. The junction experiment distinguishes mobile surface redox sites from energetically distinct deeper-sitting ‘trapped states’.
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