Interfacial structure of atomically flat polycrystalline Pt electrodes and modified Sauerbrey equation

Abstract

The electrochemical quartz-crystal nanobalance (EQCN) measures in situ mass changes associated with interfacial electrode processes. Real electrodes are not atomically flat, thus their surface roughness affects the conversion of frequency variations (Δf) to mass changes (Δm) associated with electrochemical processes. Here, we analyze Δm associated with the electrochemical H adsorption/desorption and surface oxide formation/reduction on Pt electrodes of gradually increasing surface roughness using the EQCN and cyclic-voltammetry in an aqueous H₂SO₄ solution. These two interfacial processes are ideal to probe changes in the electrochemically active surface area. The surface roughness of Pt-coated resonators is fine-tuned through Pt electrodeposition and examined using atomic force microscopy. The results acquired using Pt electrodes of increasing roughness factor (1.61 ≤ R ≤ 13.0) reveal a linear relationship between Δm and R. Extrapolation of this relationship to R = 1.00 leads to the determination of Δm associated with H adsorption/desorption and oxide formation/reduction on an atomically flat polycrystalline Pt electrode. The values of Δm associated with these processes are analyzed in terms of the number of H, O, water, and ionic species interacting with each Pt atom of the electrode surface. We find that the charge densities associated with these electrochemical processes and mass variations do not scale up by the same factor. This leads to a modified version of the Sauerbrey equation for Pt electrodes, which takes into account the intrinsic surface roughness.