Electrodeposition of Ni/Cu Bimetallic Conductive Metal–Organic Frameworks Electrocatalysts with Boosted Oxygen Reduction Activity for Zinc–Air Batteries

Abstract Zinc–air batteries employing non‐Pt cathodes hold significant promise for advancing cathodic oxygen reduction reaction (ORR). However, poor intrinsic electrical conductivity and aggregation tendency hinder the application of metal–organic frameworks (MOFs) as active ORR cathodes. Conductive MOFs possess various atomically dispersed metal centers and well‐aligned inherent topologies, eliminating the additional carbonization processes for achieving high conductivity. Here, a novel room‐temperature electrochemical cathodic electrodeposition method is introduced for fabricating uniform and continuous layered 2D bimetallic conductive MOF films cathodes without polymeric binders, employing the organic ligand 2,3,6,7,10,11‐hexaiminotriphenylene (HITP) and varying the Ni/Cu ratio. The influence of metal centers on modulating the ORR performance is investigated by density functional theory (DFT), demonstrating the performance of bimetallic conductive MOFs can be effectively tuned by the unpaired 3d electrons and the Jahn–Teller effect in the doped Cu. The resulting bimetallic Ni 2.1 Cu 0.9 (HITP) 2 exhibits superior ORR performance, boasting a high onset potential of 0.93 V. Moreover, the assembled aqueous zinc–air battery demonstrates high specific capacity of 706.2 mA h g −1 , and exceptional long‐term charge/discharge stability exceeding 1250 cycles.