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 m2 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.