Electrochemical reduction of thin graphene-oxide films in aqueous solutions: restoration of conductivity

TL;DR

This study investigates the electrochemical reduction of graphene oxide films, revealing how electrolyte choice influences reduction potential, and shows that reduction begins locally with conductive islands forming and growing, which can be controlled for specific applications.

Contribution

It provides detailed insights into the local reduction mechanism of GO and the influence of electrolytes, combining experimental and theoretical approaches to enhance control over GO reduction.

Findings

Electrolyte type affects reduction potential range.

Reduction initiates locally with conductive islands.

Activation energy is below 30 kJ/mol, lower than thermal reduction.

Abstract

Graphene oxide finds applications in different fields of science, including energy conversion. Electrochemical reduction of graphene oxide (GO) significantly improves its conductivity. However, the kinetics of this process depends on the solvent, supporting electrolyte, pH, and numerous other factors. Most studies report the macroscopic views and ex-situ properties of reduced GO. To expand the knowledge about GO reduction, in this study, we used cyclic voltammetry (CV), simultaneous 2 points and 4 points resistance measurement (s24), conductive atomic force microscopy (AFM), and theoretical calculations. Using CV, we demonstrated that the choice of supporting electrolyte (KCl or LiCl) influences the potential range in which electrochemical GO reduction occurs. The activation energy of this process was estimated to be below 30 kJ mol-1 in both electrolytes, being significantly lower than that required for thermal reduction of GO. Simultaneous in situ s24 resistance measurements suggest that GO films reach a highly conductive state at deep negative potentials, with an abrupt, irreversible switch from non-conductive to the conductive state. However, conductive AFM presents a more exact picture of this process: the reduction of GO films starts locally while the formed conductive islands grow during the reduction. This mechanism was confirmed by theoretical calculations indicating that the reduction starts on isolated oxygen-functional groups over the GO basal plane, while clustered OH groups are more difficult to reduce. The presented results can help in tailoring reduced GO for a particular electrochemical application by precisely controlling the reduction degree and percentage of the conductive area of the reduced GO films.