Insights into the Voltammetry of Cavity Microelectrodes Filled with Metal Powders: The Value of Square Wave Voltammetry

Cavity MicroElectrodes (CMEs) offer a valuable platform to evaluate the electrocatalytic performance of micro-and nano-particulate materials. The technical factors and physicochemical processes affecting electrochemical response at CMEs are be recognized, specifically, accessibility redox species electrocatalyst surface. With this aim, voltammetric is investigated through joint experimental theoretical approach including comparative study cyclic square wave voltammetry (SWV). Experiments reveal capacitive distortion that increases with powder surface area, but faradaic analogous recessed or inlaid microdisks, i.e. reactions occurring essentially on first layer load. We show SWV well suited discriminate Faradaic we present accurate mathematical expressions describe it. These results provide guidelines for design analysis CME measurements.