▎ 摘　　要

The ability to protect materials from fire is vital to many industrial applications and life safety systems. Although various chemical treatments and protective coatings have proven effective as flame retardants, they provide only temporary prevention, as they do not change the inherent flammability of a given material. In this study, we demonstrate that a simple change of the microstructure can significantly boost the fire resistance of an atomically thin material well above its oxidation stability temperature. We show that freestanding graphene layers arranged in a three-dimensional (3D) cellular network exhibit completely different flammability and combustion rates from a graphene layer placed on a substrate. Covalently cross-linked cellular graphene aerogels can resist flames in air up to 1500 degrees C for a minute without degrading their structure or properties. In contrast, graphene on a substrate ignites immediately above 550 degrees C and burns down in a few seconds. Raman spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric studies reveal that the exceptional fire-retardant and self-extinguishing properties of cellular graphene originate from the ability to prevent carbonyl defect formation and capture nonflammable carbon dioxide gas in the pores. Our findings provide important information for understanding graphene's fire-retardant mechanism in 3D structures/assemblies, which can be used to enhance flame resistance of carbon-based materials, prevent fires, and limit fire damage.