Vapor-Phase Polymerization and Carbonization to Nitrogen-Doped Carbon Nanoscale Networks with Designable Pore Geometries Templated from Block Copolymers

3D interconnected nitrogen-doped carbon nanoscale networks (N-CNNs) with designable pore geometries are prepared by vapor-phase polymerization approach and subsequent carbonization using self-assembled block copolymer (BCP) polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with bicontinuous structures as templates. PS-b-P4VP monolithic membranes composed of interconnected micellar fibers or spheres with PS@P4VP core–shell structure are obtained by swelling lamellar supramolecular membranes of PS-b-P4VP and 3-n-pentadecylphenol (PDP) via hydrogen bonding. Importantly, the morphologies of self-assembled BCP can be tuned by just adjusting swelling time for the same PS-b-P4VP(PDP). The vapor-phase polymerization strategy is adopted for the first time to complex iodine to P4VP shell layers and subsequently initiates the polymerization of pyrrole to form polypyrrole on the outside of PS@P4VP core–shell structures. After carbonization, the BCP templates are removed and N-CNNs with different pore geometries are obtained. The interconnected network structures and the introduction of nitrogen in carbon nanoscale networks make them particularly promising in many applications such as oxygen reduction reaction (ORR). The N-CNN templated from micellar fibers (N-CNN-F), as a metal-free ORR catalyst, displays comparable performance with Pt/C in alkaline media. The study provides not only a new synthesis method, but also important insight into designing 3D networks with open-celled pores for ORR and other applications.