Mapping Electroactivity at Individual Catalytic Nanostructures Using High-Resolution Scanning Electrochemical Scanning Ion Conductance Microcopy

Combined scanning electrochemical-scanning ion conductance microcopy (SECM-SICM) has been used to map the electroactivity of surfaces decorated with individual features at the 100-150 nm scale. Dual channel capillary probes consisting of an open SICM barrel, and a solid carbon SECM electrode enabled correlation of surface activity with accurate topographical information. Measurements were validated by approach curve analysis and imaging of model systems in feedback and substrate generation-tip collection modes and then applied to the examination of two nanostructured test substrates. First, electronically isolated gold nanodisk arrays were imaged using a simple electrochemical redox mediator, in which a clear positive feedback signal was observed at the SECM electrode, and the topographical channel compared well with AFM imaging. Second, platinum nanosphere ensembles were mapped using platinum-modified carbon probes to detect oxygen consumption in a redox competition mode, demonstrating the means to study electrocatalytic processes at individual nanoparticles. This work demonstrates the value of high-resolution SECM-SICM for low-current amperometric imaging of nanosystems, and is a step toward quantitative measurement of electrokinetics at the single particle level.