Abstract
A mesopore-rich, hierarchically porous carbon monolith was prepared by carbonizing a polyisocyanurate network derived by thermal rearrangement of a polyurea network. The initial polyurea network was synthesized by the cross-linking polymerization of tetrakis(4-aminophenyl)methane (TAPM) and hexamethylene diisocyanate (HDI) in the sol-forming condition, followed by precipitation into nanoparticulate solids in a nonsolvent. The powder was molded into a shape and then heated at 200-400 °C to obtain the porous carbon precursor composed of the rearranged network. The thermolysis of urea bonds to amine and isocyanate groups, the subsequent cyclization of isocyanates to isocyanurates, and the vaporization of volatiles caused sintering of the nanoparticles into a monolithic network with micro-, meso-, and macropores. The rearranged network was carbonized to obtain a carbon monolith. It was found that the rearranged network, with a high isocyanurate ratio, led to a porous carbon with a high mesopore ratio. The electrical conductivity of the resulting carbon monoliths exhibited a rapid response to carbon dioxide adsorption, indicating efficient gas transport through the hierarchical pore structure.