Individual Nanoporous Carbon Spheres with High Nitrogen Content from Polyacrylonitrile Nanoparticles with Sacrificial...

Functional nanoporous carbon spheres (NPC-S) are important for applications ranging from adsorption, catalysis, separation to energy storage, and biomedicine. The development of effective NPC-S materials has been hindered by the fusion of particles during the pyrolytic process that results in agglomerated materials with reduced activity. Herein, we present a process that enables the scalable synthesis of dispersed NPC-S materials by coating sacrificial protective layers around polyacrylonitrile nanoparticles (PAN NPs) to prevent interparticle cross-linking during carbonization. In a first step, PAN NPs are synthesized using miniemulsion polymerization, followed by grafting of 3-(triethoxysilyl)propyl methacrylate (TESPMA) to form well-defined core-shell structured PAN@PTESPMA nanospheres. The cross-linked PTESPMA brush layer suppresses cross-linking reactions during carbonization. Uniform NPC-S exhibiting diameters of ∼100 nm, with relatively high accessible surface area (∼424 m²/g), and high nitrogen content (14.8 wt %) was obtained. When compared to a regular nanoporous carbon monolith (NPC-M), the nitrogen-doped NPC-S demonstrated better performance for CO₂ capture with a higher CO₂/N₂ selectivity, an increased efficiency in catalytic oxygen reduction reactions, as well as improved electrochemical capacitive behavior. This miniemulsion polymerization-based strategy for the preparation of functional PAN NPs provides a new, facile approach to prepare high-performance porous carbon spheres for diverse applications.