High-Throughput Correlative Electrochemistry–Microscopy at a Transmission Electron Microscopy Grid Electrode

As part of the revolution in electrochemical nanoscience, there is growing interest in using electrochemistry to create nanostructured materials and to assess properties at the nanoscale. Herein, we present a platform that combines scanning electrochemical cell microscopy with ex situ scanning transmission electron microscopy to allow the ready creation of an array of nanostructures coupled with atomic-scale analysis. As an illustrative example, we explore the electrodeposition of Pt at carbon-coated transmission electron microscopy (TEM) grid supports, where in a single high-throughput experiment it is shown that Pt nanoparticle (PtNP) density increases and size polydispersity decreases with increasing overpotential (i.e., driving force). Furthermore, the coexistence of a range of nanostructures, from single atoms to aggregates of crystalline PtNPs, during the early stages of electrochemical nucleation and growth supports a nonclassical aggregative growth mechanism. Beyond this exemplary system, the presented correlative electrochemistry-microscopy approach is generally applicable to solve ubiquitous structure-function problems in electrochemical science and beyond, positioning it as a powerful platform for the rational design of functional nanomaterials.