Unpaired 3d Electrons on Atomically Dispersed Cobalt Centres in Coordination Polymers Regulate both Oxygen Reduction Reaction (ORR) Activity and Selectivity for Use in Zinc–Air Batteries

Reversible oxygen conversion is important for various green energy technologies. Herein we synthesize a series of bimetallic coordination polymers by varying the Ni/Co ratio and using HITP (HITP=2,3,6,7,10,11‐hexaiminotriphenylene) as the ligand, to interrogate the role of metal centres in modulating the activity of the oxygen reduction reaction (ORR). Co 3 HITP 2 and Ni 3 HITP 2 are compared. Unpaired 3d electrons in Co 3 HITP 2 result in less coplanarity but more radical character. Thus, despite of a reduced crystallinity and conductivity, the best ORR activity, comparable to 20 % Pt/C, is obtained for Co 3 HITP 2 , showing the 3d orbital configuration of the metal centre promotes ORR. Experimental and DFT studies show a transition of ORR pathway from four‐electron for Co 3 HITP 2 to two‐electron for Ni 3 HITP 2 . Rechargeable zinc–air batteries using Co 3 HITP 2 as the air cathode catalyst demonstrate excellent energy efficiency and stability.