Electronic Structure Tunable Metallosupramolecular Polymers as Bifunctional Electrocatalysts for Rechargeable Zn‐Air Battery

Abstract Metallosupramolecular polymers (MSPs) have shown great potential in the area of oxygen electrocatalysis due to their tunable electronic structure, and predictable coordination environment. Further exploration of structure−performance relationships of oxygen electrocatalysts is crucial for designing highly efficient catalysts. Herein, a strategy is proposed to prepare MSP‐based bifunctional oxygen electrocatalysts with different oxygen electrocatalytic preferences (Co‐AQ and Co‐AN) by adjusting the electronic structure of organic linkers. The electronic effects of organic linkers significantly influence the adsorbate evolution mechanism. Co‐AQ, with an electron‐withdrawing linker, demonstrated superior OER activity among the two with an overpotential of 280 mV at 10 mA cm ⁻² and 340 mV at 50 mA cm ⁻² . In contrast, Co‐AN, with an electron‐donating linker, exhibited outstanding ORR activity with a large limiting current density of 6.14 mA cm ⁻² . Furthermore, the Co‐AQ‐based Zn–air battery showed a high power density (135 mW cm ⁻² ) and excellent cycling stability of 100 h. This work presents a novel approach for adjusting bifunctional oxygen electrocatalysis performance and further reveals the structure−performance relationships of oxygen electrocatalysts.