Influence of Particle Size on Mass Transport during the Oxygen Reduction Reaction at Single Silver Particles Using Scanning Electrochemical Cell Microscopy

Single entity electrochemical measurements enable insight into the electrocatalytic activity of individual particles based on composition, shape, and crystallographic orientation. In addition to structural effects, particle size can further influence electrocatalytic activity and reaction mechanisms through mass transport effects. In this work, electrodeposition was used to grow well-separated silver particles of varying sizes from 100 to 500 nm in radius. Using a multimicroscopy approach of scanning electrochemical cell microscopy combined with scanning electron microscopy, the electrocatalytic current of individual silver particles toward the oxygen reduction reaction was evaluated as a function of their size. It was found that the current density increased with decreasing particle radius, which was correlated to the mass transport of oxygen to the silver particle, demonstrating the importance of size dependent mass transport effects that can occur at the single particle level using scanning electrochemical cell microscopy and opening new opportunities for quantitative electrocatalysis measurements.