Recent progress in the theory and practice of voltammetry is surveyed and evaluated. The transformation over the last decade of the level of modelling and simulation of experiments has realised major advances such that electrochemical techniques can be fully developed and applied to real chemical problems of distinct complexity. This review focuses on the topic areas of: multistep electrochemical processes, voltammetry in ionic liquids, the development and interpretation of theories of electron transfer (Butler–Volmer and Marcus–Hush), advances in voltammetric pulse techniques, stochastic random walk models of diffusion, the influence of migration under conditions of low support, voltammetry at rough and porous electrodes, and nanoparticle electrochemistry. The review of the latter field encompasses both the study of nanoparticle‐modified electrodes, including stripping voltammetry and the new technique of ‘nano‐impacts’.

The current state-of-the-art in modeling the rate of electron transfer between an electroactive species and an electrode is reviewed. Experimental studies show that neither the ubiquitous Butler–Volmer model nor the more modern symmetric Marcus–Hush model are able to satisfactorily reproduce the experimental voltammetry for both solution-phase and surface-bound redox couples. These experimental deviations indicate the need for revision of the simplifying approximations used in the above models. Within this context, models encompassing asymmetry are considered which include different vibrational and solvation force constants for the electroactive species. The assumption of non-adiabatic electron transfer is also examined. These refinements have provided more satisfactory models of the electron transfer process and they enable us to gain more information about the microscopic characteristics of the system by means of simple electrochemical measurements.

The electrocatalytic activity for oxygen reduction reaction (ORR) at neutral pH of citrate-capped silver nanoparticles (diameter = 18 nm) supported on glassy carbon (GC) is investigated voltammetrically. Novelly, the modification of the substrate by nanoparticles sticking to form a random nanoparticle array and the voltammetric experiments are carried out simultaneously by immersion of the GC electrode in an air-saturated 0.1 M NaClO₄ solution (pH = 5.8) containing chemically-synthesized nanoparticles. The experimental voltammograms of the resulting nanoparticle array are simulated with homemade programs according to the two-proton, two-electron reduction of oxygen to hydrogen peroxide where the first electron transfer is rate determining. In the case of silver electrodes, the hydrogen peroxide generated is partially further reduced to water via heterogeneous decomposition. Comparison of the results obtained on a silver macroelectrode and silver nanoparticles indicates that, for the silver nanoparticles and particle coverages (0.035%–0.457%) employed in this study, the ORR electrode kinetics is slower and the production of hydrogen peroxide larger on the glassy carbon-supported nanoparticles than on bulk silver.