Functionality Modulation Toward Thianthrene‐based Metal‐Free Electrocatalysts for Water Splitting

Abstract The development of metal‐free bifunctional electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER) is significant but rarely demonstrated. Porous organic polymers (POPs) with well‐defined electroactive functionalities show superior performance in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Precise control of the active sites' local environment requires careful modulation of linkers through the judicious selection of building units. Here, a systematic strategy is introduced for modulating functionality to design and synthesize a series of thianthrene‐based bifunctional sp² C═C bonded POPs with hollow spherical morphologies exhibiting superior electrocatalytic activity. This precise structural tuning allowed to gain insight into the effects of heteroatom incorporation, hydrophilicity, and variations in linker length on electrocatalytic activity. The most efficient bifunctional electrocatalyst THT‐PyDAN achieves a current density of 10 mA cm^─2 at an overpotential (η₁₀) of ≈65 mV (in 0.5 m H₂SO₄) and ≈283 mV (in 1 m KOH) for HER and OER, respectively. THT‐PyDAN exhibits superior activity to all previously reported metal‐free bifunctional electrocatalysts in the literature. Furthermore, these investigations demonstrate that THT‐PyDAN maintains its performance even after 36 h of chronoamperometry and 1000 CV cycling. Post‐catalytic characterization using FT‐IR, XPS, and microscopic imaging techniques underscores the long‐term durability of THT‐PyDAN.