TG curve of resultant composite in nitrogen atmosphere shows that approximately 49 wt% weight
loss occurred in the temperature range of 350–450 C, corresponding to the partial decomposition of melamine sponge
and block copolymer. Therefore, composite pyrolyzed at as low as 350 C can remove skeleton structure to fabricate hierarchical porous structure. Subsequently, a continuous slower weight loss of composite occurs in the range of 450–800 C,which is similar to the degradation behavior of phenolic resin.With good thermostability and high carbon content, phenolic resin can act as skeleton to support the hierarchical porousstructure, and finally convert into carbonaceous components of macro/mesoporous monolith. Meanwhile, the decomposition behavior of carbon monolith in air is shown in Fig. 5b.The weight loss of C-1000 sample is only 8 wt% at 500 C,mainly resulting from the removal of water absorbed on porous structure as well as the destruction of labile oxygen-containing functional groups in the sample [21]. Therefore, when C-1000 sample is exposed to the flame of alcohol burner, it can keep from combustion and remain inert, suggesting
superior fire-resistant property (see the inset in Fig. 5b and Movie S1).