Composite materials and methods of preparing C02 capture include: (1) a porous solid support comprising a plurality of porous channels; and (2) a nucleophilic source associated with the porous channels of the porous solid support. The nucleophilic source is capable of converting the captured C02 to poly(C02). Methods of capturing C02 from an environment include associating the environment with the aforementioned composite materials to lead to the capture of C02 from the environment. Such methods may also include a step of releasing the captured C02 from the composite material. The associating step comprises a conversion of the captured C02 to poly(C02) in the composite material. A releasing step may also include a depolymerization of the formed poly(C02).