▎ 摘　　要

Currently, researchers are paying much attention to the development of effective 3D graphene for applications in energy storage and environmental purification. Before commercialization, however, it is necessary to develop a method that allows for the large-scale production of such materials and enables good control over their structural and chemical properties. With this objective, we herein developed a simple method for the formation of large-scale (4 in. wafer) 3D graphene networks via the self-assembly of graphene sheets at a superheated liquid-vapor interface. The structural morphology of this porous network could be modified by controlling the vaporization rate, surface temperature of the target substrate, and amount of discharged colloids. The key mechanism behind this intriguing result was investigated by high-speed visualization of microdroplet behavior and extensive thermal analysis. This self-assembled 3D graphene had excellent electrical and mechanical properties. Our approach can be directly used for the mass production of graphene-based materials.