Cross-Linked Polyphosphazene Hollow Nanosphere-Derived N/P-Doped Porous Carbon with Single Nonprecious Metal Atoms for the Oxygen Reduction Reaction

Heteroatom-doped polymers or carbon nanospheres have attracted broad research interest. However, rational synthesis of these nanospheres with controllable properties is still a great challenge. Herein, we develop a template-free approach to construct cross-linked polyphosphazene nanospheres with tunable hollow structures. As comonomers, hexachlorocyclotriphosphazene provides N and P atoms, tannic acid can coordinate with metal ions, and the replaceable third comonomer can endow the materials with various properties. After carbonization, N/P-doped mesoporous carbon nanospheres were obtained with small particle size (≈50 nm) and high surface area (411.60 m² g⁻¹). Structural characterization confirmed uniform dispersion of the single atom transition metal sites (i.e., Co-N₂P₂) with N and P dual coordination. Electrochemical measurements and theoretical simulations revealed the oxygen reduction reaction performance. This work provides a solution for fabricating diverse heteroatom-containing polymer nanospheres and their derived single metal atom doped carbon catalysts.