▎ 摘　　要

Graphene is a promising support for nanosized electrocatalysts, however the conventional stacking arrangement of its graphene sheets substantially decreases the catalytic sites on the catalyst. We report here the fabrication of a graphene/Cu electrocatalyst by the simple cyclic voltammetric electrolysis of graphene oxide (GO) and copper ethylenediamine tetraacetate (Cu-EDTA), and find that the electrochemically reduced GO (RGO) and Cu nanoparticles can be sequentially self-assembled into layer-by-layer, 3D sandwich-type, and homogenous architectures as the concentration ratio of Cu-EDTA/GO increases. The 3D sandwich-type RGO/Cu composite (S-RGO/Cu) shows RGO sheets decorated with Cu nanoparticles which stand nearly perpendicular on the electrode, leading to a significant increase in the electrochemically accessible surface area (0.685 cm(2)) relative to those of the horizontal layer-by-layer RGO/Cu composite (0.147 cm(2)) and the homogenous RGO/Cu composite (0.265 cm(2)). Stemming from its high electrochemical surface area, the S-RGO/Cu composite exhibits a high electrocatalytic activity in hydrazine oxidation in terms of current density and overpotential. Mechanistic analysis of the electrode reactions reveals the reaction pathways of hydrazine on RGO/Cu are closely related to the electrochemical surface area of the RGO/Cu electrocatalyst. The correlation between the architectures and their performances in electrocatalysis presented here can guide the design of novel structures with enhanced properties.