General Formation of Macro‐/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra‐large open channels in their nanoshells are of great interest. However, soft template‐directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro‐/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N‐doped macro‐/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition. A universal irregular‐type mesostructured nanounit assembly method is developed to form hierarchically macro‐/mesoporous polymer and carbon nanoshells on various functional materials. With structural and compositional advantages, Fe,N‐doped porous carbon nanoshells exhibit enhanced electrocatalytic performance for the oxygen reduction reaction in an alkaline electrolyte.