Monomicellar Assembly for Hierarchically Meso‑Macroporous Spheres

Hierarchically meso‐macroporous materials are attractive for catalysis, separations, and energy conversion, yet controlling multiple pore length scales within a single soft‐template system remains challenging. Here, we develop a molecularly guided monomicellar assembly strategy that couples amine‐mediated interfacial polymerization with molecular engineering of polyphenol precursors to construct hierarchically meso‐macroporous spheres. We show that precursor‐micelle interactions and solvent‐regulated interfacial dynamics govern the transition from individual micelle templating to intermicellar collision and fusion, allowing micelle‐derived mesopores to be preserved while larger macroporous domains are generated. Tuning the interactions enables programmable pore evolution from surface‐mesoporous and multichambered mesoporous architectures to hierarchically meso‐macroporous spheres. The resulting nitrogen‐doped carbon spheres possess uniform sizes (∼355 nm), high surface areas (379.2 m 2 g −1 ), and well‐defined hierarchical pore networks (∼36, ∼62, and ∼121 nm). As metal‐free electrocatalysts, they exhibit enhanced oxygen reduction activity. Our findings establish a general design principle for extending monomicellar assembly from mesoporous materials to hierarchical porous architectures and provide new opportunities for the rational synthesis of multi‐scale porous materials.