Scanning Bubble Electrochemical Microscopy: Mapping of Electrocatalytic Activity with Low-Solubility Reactants.

Determining electrocatalytic activity for reactions that involve reactants with limited solubility presents a significant challenge due to the reduced mass-transport to the electrocatalyst surface. This limitation is seen in important reactions such as the oxygen reduction reaction, nitrogen reduction reaction, and carbon dioxide reduction reaction. We introduce a new approach, which we call scanning bubble electrochemical microscopy, to enable the detection and high-resolution mapping of electrocatalytic activity with low-solubility reactants at high mass-transport rates. Using a scanning probe approach, a dual-barreled nanopipette is used to precisely deliver the gas-phase reactant within micrometers of an electrocatalyst surface, which results in high mass-transport rates at the electrocatalyst surface directly under the probe. We demonstrate the scanning bubble electrochemical microscopy approach by mapping the oxygen reduction reaction on model platinum microelectrode surfaces. We anticipate that scanning bubble electrochemical microscopy will provide an effective tool for measuring the electrocatalytic activity of reactants that have limited solubility.