Engineering p‐Orbital States via Molecular Modules in All‐Organic Electrocatalysts toward Direct Water Oxidation

Oxygen evolution reaction (OER) is an indispensable anode reaction for sustainable hydrogen production from water electrolysis, yet overreliance on metal-based catalysts featured with vibrant d-electrons. It still has notable gap between metal-free and metal-based electrocatalysts, due to lacking accurate and efficient p-band regulation methods on non-metal atoms. Herein, a molecular modularization strategy is proposed for fine-tuning the p-orbital states of series metal-free covalent organic frameworks (COFs) for realizing OER performance beyond benchmark precious metal catalysts. Optimized combination of benzodioxazole/benzodiimide-based building blocks achieves an impressive applied potential of 1.670 ± 0.004 V versus reversible hydrogen electrode (RHE) and 1.735 ± 0.006 V versus RHE to deliver enhanced current densities of 0.5 and 1.0 A cm