Diffusion Models of Mass Transport for the Characterisation of Amperometric Gas Sensors

\ua9 2024 The Authors. ChemElectroChem published by Wiley-VCH GmbH. A diffusion model for the analysis of chronoamperometric data in response to a concentration step is developed for amperometric gas sensors. This analysis avoids the difficulties with standard potentiodynamic measurements at the large specific area, high capacitance electrodes employed in these sensors. Despite the fact that typical devices comprise multiple layers with varying thicknesses and diffusivities, we show that typical chronoamperometric traces can be fitted to a simple diffusion model with a single parameter (Formula presented.) where L is an overall effective thickness of the diffusion barrier and D is an effective diffusion coefficient. Through a comparison of the transient and steady-state current, independent estimates of L and D in the devices can be made. The model is also extended to cover cases with interfacial kinetic barriers; such kinetic limitations lead to a change in the effective values L and D, but the simple diffusion model remains a good fit to the data. This analysis shows that transient sensor responses can be characterised by a single parameter τ and conversely that deviations from this regression model cannot be assigned to (i) complex layer architectures or (ii) interlayer kinetic barriers. Instead, we show that non-uniform accessibility effects arising from a distribution of diffusion rates across the device lead to deviations from the simple regression model, but that they may be captured approximately by a more complex model in which τ has a probability distribution