Frontiers in Nanoscale Electrochemical Imaging: Faster, Multifunctional, and Ultrasensitive

A wide range of interfacial physicochemical processes, from electrochemistry to the functioning of living cells, involve spatially localized chemical fluxes that are associated with specific features of the interface. Scanning electrochemical probe microscopes (SEPMs) represent a powerful means of visualizing interfacial fluxes, and this Feature Article highlights recent developments that have radically advanced the speed, spatial resolution, functionality, and sensitivity of SEPMs. A major trend has been a coming together of SEPMs that developed independently and the use of established SEPMs in completely new ways, greatly expanding their scope and impact. The focus is on nanopipette-based SEPMs, including scanning ion conductance microscopy (SICM), scanning electrochemical cell microscopy (SECCM), and hybrid techniques thereof, particularly with scanning electrochemical microscopy (SECM). Nanopipette-based probes are made easily, quickly, and cheaply with tunable characteristics. They are reproducible and can be fully characterized. Their response can be modeled in considerable detail so that quantitative maps of chemical fluxes and other properties (e.g., local charge) can be obtained and analyzed. This article provides an overview of the use of these probes for high-speed imaging, to create movies of electrochemical processes in action, to carry out multifunctional mapping such as simultaneous topography-charge and topography-activity, and to create nanoscale electrochemical cells for the detection, trapping, and analysis of single entities, particularly individual molecules and nanoparticles (NPs). These studies provide a platform for the further application and diversification of SEPMs across a wide range of interfacial science.