▎ 摘　　要

High-temperature annealing is an effective way to heal the defects of graphene-based nanocarbons and enhance their crys-tallinity. However, the thermally induced vibration of the graphene building blocks often leads to unfavorable micro-, nano-structural evolution including layer stacking. Herein, the key structural factors to achieve highly crystalline graphene frameworks with desired microstructures upon annealing at 1800 & DEG;C is revealed. The structural changes of fullerenes,single-walled carbon nanotubes, and graphene-based porous frameworks are precisely analyzed by their structural parame-ters, such as the total number of graphene edge sites and precise graphene stacking structures, using a novel advanced vacuum temperature-programmed desorption technique up to 1800 & DEG;C. The stacked structure is differentiated into loose and tightly stacking, where the loosely stacked structure is found to induce further stacking at high-temperature. Moreover, a graphene framework with an inner space size of greater than 4-7 nm isbeneficial to avoid structural change upon high-temperature annealing. These findings offer both a fundamental under-standing of the solid-state chemistry of nanocarbons under high temperatures and a viable strategy for engineering edge-site free graphene frameworks with pre-designed microstructures.