Electrochemistry at 2D and 3D nanoelectrodes: The interplay between interface kinetics and surface density of states

Abstract

Heterogenous Electron Transfer (HET) at electrode-electrolyte interfaces depends strongly on the morphological features or geometry of the nanostructure used for modifying the electrode surface. A swift HET results in faster interface kinetics, which has significant impact on the development/calibration of electrochemical devices like biomolecular sensors, supercapacitors, batteries and electrochromic platforms. The interface electrochemistry depends strongly on the electronic Density of States (DOS) of electrode materials. Over the past years, the 2D electron gas nanomaterials - primarily graphene, Graphene Oxide (GO) and Reduced Graphene Oxide (RGO), have garnered significant interest in electrochemical applications due to promising DOS features. However, the electroanalytical dependency on DOS of 3D nanostructures such as Zinc Oxide Tetrapods (ZnOT) is yet unexplored. The current work focusses on a comparative electrochemical analysis of interface kinetics at RGO (2D) and ZnOT (3D) coated screen printed electrodes, with the intention of selecting the suitable material geometry. The analyses were performed using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). While the dependence of HET on DOS of RGO and ZnOT nanomaterials were studied using both DFT analysis and impedance-derived capacitance spectroscopy – the latter giving insights on quantum capacitance. It was observed that, the 2D RGO nanostructures exhibit higher surface DOS near the Fermi level, along with a high quantum capacitance (∼345 nF) as compared to 3D ZnOT (∼276 nF). This results in enhanced HET at the former, thereby indicating its suitability in developing futuristic electrochemical devices for various applications as desired.