A porous polymer aerogel, wherein the aerogel has greater than 5 wt % of amine containing vinyl monomers integrated into a polymer backbone. A method of fabrication of a porous polymer aerogel amine material, includes preparing a solution comprising at least a solvent, amine monomers having protected amino groups, one or more crosslinkers, one or more radical initiators, and a nitroxide mediator, removing oxygen from the solution, heating the solution to promote polymerization and to produce a polymerized material, performing solvent exchange with the polymerized material, causing a deprotection reaction in the polymerized material to remove groups protecting the amino groups, soaking and rinsing the material to remove excess reagents and any byproducts of the deprotection reaction, and drying the material to produce the amine sorbent. A system to separate CO2 from other gases, comprising a polymer porous aerogel sorbent having greater than 5 wt % of amine containing vinyl monomers integrated into a polymer backbone.