d-Orbital steered active sites through ligand editing on heterometal imidazole frameworks for rechargeable zinc-air battery

The implementation of pristine metal-organic frameworks as air electrode may spark fresh vitality to rechargeable zinc-air batteries, but successful employment is rare due to the challenges in regulating their electronic states and structural porosity. Here we conquer these issues by incorporating ligand vacancies and hierarchical pores into cobalt-zinc heterometal imidazole frameworks. Systematic characterization and theoretical modeling disclose that the ligand editing eases surmountable energy barrier for *OH deprotonation by its efficacy to steer metal d-orbital electron occupancy. As a stride forward, the selected cobalt-zinc heterometallic alliance lifts the energy level of unsaturated d-orbitals and optimizes their adsorption/desorption process with oxygenated intermediates. With these merits, cobalt-zinc heterometal imidazole frameworks, as a conceptually unique electrode, empowers zinc-air battery with a discharge-charge voltage gap of 0.8V and a cyclability of 1250h at 15mAcm(-2), outperforming the noble-metal benchmarks. Low intrinsic activity and accessibility of active sites limit the application of metal-organic framework as catalyst for Zn-air battery. Here, authors present a cation substitution strategy to regulate the electronic state of metal sites and modify its porosity, which enables battery operation.