Electron Localization Engineering of Ordered Macro‐Microporous 2D Conjugated Metal–Organic Frameworks for Efficient Bifunctional Oxygen Electrocatalysis

The rational synthesis of ordered macro‐microporous 2D conjugated metal–organic frameworks (2D conjugated MOFs) is crucial yet challenging to overcome mass transport limitations and enhance active site accessibility in electrocatalysis. Herein, a universal ligand‐switched architecture duplication strategy is reported for constructing ordered macro‐microporous 2D conjugated MOFs. Through utilizing this strategy, the ordered macro‐microporous insulating MOF precursors are transformed into highly conductive analogues featuring hierarchical ordered porosity with ultrathin nanosheet subunits (1.5 nm), high specific surface areas (803.7 m 2 g −1 for OM Co‐HITP), and significantly enhanced electrical conductivity (0.13 S cm −1 , an order of magnitude higher than bulk counterpart). Furthermore, the precise modulation of Co‐site electron localization via concentration‐dependent sodium oxalate treatment enables controlled formation of Co 2 + /Co 3 + mixed‐valence states. The as‐resulted catalyst exhibits exceptional bifunctional activity for oxygen evolution and reduction reactions (OER/ORR) via 4e − pathways, with an OER overpotential of 237 mV at 10 mA cm −2 in 1 m KOH and an ORR half‐wave potential of 0.834 V (vs. RHE). DFT calculations reveal that the modulation of the Co‐site electronic structure reduces OOH * formation energy, enhancing activity by optimizing intermediate adsorption. This work provides new insights into designing efficient bifunctional electrocatalysts through synergistic pore and electronic structure regulation.