Topological Control over Porphyrin‐Based Covalent Organic Frameworks for Elucidating Electron Transfer Characteristics

Two‐dimensional covalent organic frameworks (2D COFs) have emerged as promising functional materials due to their programmable architectures and tunable functionalities. Nevertheless, the structural diversity of porphyrin‐based 2D COFs remains restricted by the prevalent use of sql topology, hindering comprehensive structure‐property exploration. Herein, we systematically designed and synthesized porphyrinic 2D COFs featuring distinct sql and bex topological configurations. Comprehensive structural characterization confirmed precise control over lattice geometries, revealing monoporous structure in sql topology versus biporous architecture in bex topology. Electrochemical investigations uncovered topologygoverned electron transport characteristics, with the unique coordination geometry of bex topology exhibiting enhanced electron transfer efficiency. Band structure analysis demonstrated that topological configuration and chemical composition collectively modulate electronic structures. Inspired by these findings, we developed nickel‐incorporated bex‐COFs for electrocatalytic oxygen evolution. The optimized Ni‐BBFPP‐TAPP‐COF with bex topology demonstrated remarkable catalytic performance, achieving a low overpotential of 342 mV at 10 mA cm−2, which surpasses most reported porphyrin‐based electrocatalysts. This study not only significantly expands the structural repertoire of porphyrinic COFs, but also establishes explicit correlations between topological engineering and electrocatalytic performance, providing fundamental design principles for advanced energy conversion materials.