Homogeneous Template‐Directed Synthesis of Hollow Porous Nitrogen‐Rich Conjugated Polymers with Adjustable Mesopore to Macropore

ABSTRACT Hollow porous structures can endow materials with exceptional properties, thus stimulating widespread interest in various fields such as energy storage, adsorption, catalysis, and drug delivery. Despite considerable progress, the bottom‐up synthesis of hollow porous superparticles with controlled morphology and broadly tunable pore sizes using only a single type of template still remains a significant challenge. Herein, we develop a homogeneous template‐directed (HTD) strategy using monocomponent templates with a bimodal size distribution to synthesize well‐defined hollow porous superparticles. The large and small templates, respectively construct the macroporous hollow cavity and the meso‐/macroporous shell, achieving broad pore size tunability. Based on electrostatic assistance and polymerization‐induced co‐assembly (PICA), this approach yields a central cavity (∼400 nm) and an outer shell of multi‐layered, closely‐packed spherical meso/macropores (tunable from ∼7 nm to 100 nm), thereby achieving simultaneous control over both morphology and pore size. Density functional theory (DFT) calculations and systematic experimental results reveal that the as‐synthesized superparticles can effectively immobilize iodine and suppress the shuttle effect through the synergistic effect of their hollow porous structure and the strong adsorption provided by nitrogen‐rich sites, which makes them excellent iodine hosts, thus leading to remarkable electrochemical performance in zinc‐iodine batteries (an initial capacity of 229.4 mAh g −1 at 1.0 A g −1 and a retention of 137.6 mAh g −1 after 5000 cycles). This work will open a new avenue for the controlled co‐assembly synthesis of superparticles toward energy storage and beyond.