Designing Salen‐Based Porous Organic Polymers for Enhanced Electrolytic Water Splitting into Oxygen

The development of electricity‐driven oxygen evolution reaction (OER) is a potent solution for energy storage applications. In recent years, there is a surge in interest in designing transition metal‐based catalysts with stable linkages, presenting an efficient alternative to noble metal‐based electrocatalysts. Transition metal complexes linked by salen ligands garner considerable attention due to their capacity to chelate and stabilize metal ions. This work presents a novel approach by strategically incorporating the metal–salen core into a porous organic polymer (POP) backbone, thereby fabricating a highly effective electrocatalyst for oxygen evolution. The judicious selection of metal–salen active sites, coupled with the intramolecular free volume (IMFV) of the triptycene core and the high specific surface area of the salen–POPs, result in superior OER activity. By precisely tuning the structure through variation of the transition metal in the salen unit, deep insights are gained into their electrocatalytic behavior. Notably, the most efficient catalyst, Ni‐DHDA‐TAT, exhibits an impressively low overpotential (η10) of ≈ 270 mV at a current density of 10 mA cm−2 for OER (in 1 m KOH). Further, Ni‐DHDA‐TAT retains its activity even after 50 h of chronoamperometry and 1000 cyclic voltammetry cycles with negligible degradation in its initial performance. A series of porous organic polymers with a metal–salen core is constructed as an efficient electrocatalyst for oxygen evolution from water. Various transition metals in the salen pockets act as a primary active site for the interaction of active intermediates. Bent Triptycene moiety having intramolecular free volume creates microporosity in polymeric framework to boost oxygen evolution.