Decoding nanoscale electrochemistry with nanoparticle impacts

Abstract

Nano-impact electrochemistry (NIE) probes electrochemical function one nanoparticle at a time. Freely diffusing particles stochastically collide with an ultramicroelectrode, and each impact produces a current transient that reports single-entity reactivity, transport and transformation. In this review, we place the impact waveform and its data processing at the centre of the discussion and use them as a common language across systems. We describe how chronoamperometric traces are transformed into standardized observables (event counts, peak or step currents, charge, lifetimes, and waiting times), and how these, in turn, enable the extraction of electron transfer kinetics, turnover metrics and transport parameters. We then connect characteristic waveform shapes to mechanistic pictures for both pure electron transfer and coupled ion–electron transfer, using a selector framework in which potential, transport geometry, local composition and reaction timescale determine which reaction pathways are expressed. Multi-collision trajectories, confinement and adsorption/ejection are discussed as elements of a nanoparticle lifecycle. Finally, we highlight how external stimuli and multimodal couplings extend NIE toward establishing correlations between structure, environment and activity and propose a roadmap that outlines key directions and challenges for advancing NIE from studies of model nanoparticles to a broadly applicable tool for complex systems and device-level design.