Asymmetric‐Wall Nanoporous Polymer Capsules via AIEgen‑Assisted Assembly as High‑Performance Electrocatalytic Carriers

ABSTRACT Soft‐templating through the co‐assembly of surfactants and precursors is a powerful strategy for synthesizing ordered porous materials. However, the range of available precursors and materials is relatively limited, and the correlation between precursor structure and the resulting morphology remains largely unexplored. Herein, we design a water‐soluble, ammonium‐functionalized aggregation‑induced emission luminogen (AIEgen) that serves dual roles as a crosslinkable building block and an auxiliary fluorescence probe. Co‑assembled with Pluronic F127 in an emulsion, this system yields an asymmetric‑wall nanoporous polymer capsule (ANPC) with a mesoporous outer shell and a dense inner layer, a morphology rarely achieved in polymer‑based systems. Multi‐scale characterizations, spanning fluorescence monitoring, precursor structure variation, electron microscopy, crystallographic and computational analyses, collectively reveal that AIEgen‑solvent and AIEgen‑F127 interactions cooperatively govern this architecture evolution. Benefiting from its hollow cavity and nanoporous shell that promote mass transport and site accessibility, the cobalt phthalocyanine‐loaded ANPC catalyst achieves an impressive methanol Faradaic efficiency of 44.2% in acidic CO 2 electroreduction, markedly outperforming nonporous bulk (6.8%), nonporous capsules (14.8%), mesoporous nanospheres (17.5%), and sparse‐porous capsules (28.5%). Ultimately, this work establishes a rational co‐assembly strategy for engineering porous architectures, highlighting how precursor design dictates morphology and how such structural uniqueness directly boosts electrocatalytic performance.