Electrochemically reduced graphene oxide (ERGO) is widely used to construct electrochemical sensors. Understanding the electron transfer behavior of ERGO is essential for its electrode material applications. In this paper, different morphologies of ERGO were prepared via two different methods. Compared to ERGO/GCEs prepared by electrochemical reduction of pre-deposited GO, more exposed edge planes of ERGO are observed on the surface of ERGO-GCE that was constructed by electrophoretic deposition of GO. The defect densities of ERGO were controlled by tuning the mass or concentration of GO. The electron transfer kinetics (k 0 ) of GCE with different ERGOs was comparatively investigated. Owing to increased surface areas and decreased defect density, the k 0 values of ERGO/GCE initially increase and then decrease with incrementing of GO mass. When the morphology and surface real areas of ERGO-GCE are the same, an increased defect density induces an accelerated electron transfer rate. k 0 valuesof ERGO-GCEs are about 1 order of magnitude higher than those of ERGO/GCEs due to the difference in the amount of edge planes. This work demonstrates that both defect densities and edge planes of ERGO play crucial roles in electron transfer kinetics.

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