Tailoring Cationic Cobalt Vacancies in Molybdenum–Cobalt Selenide Derived from POM@ZIF-67 for Enhanced Electrocatalysis in Lithium–Oxygen Batteries

Slow reaction kinetics during redox reactions limits the utilization of the high theoretical energy density of lithium-oxygen batteries (LOBs). Vacancy engineering, a potential strategy for modulating active sites, is critical in the development of high performance catalysts. This study investigates cobalt vacancies in Mo-CoSe₂ nanoparticles created by selenization of phosphomolybdic acid (POM) embedded into zeolitic imidazolate framework-67 (ZIF-67). The nanomaterial exhibits an outstanding electrochemical performance, characterized by high specific capacitance and excellent cycle durability. The LOBs with cobalt vacancies in the Mo-CoSe₂ electrode material exhibit a discharge capacity of 21 836 mAh g^-1 at a current density of 100 mA g^-1 and exhibit stable cycling performance over 194 cycles at 300 mA g^-1. Additionally, density functional theory (DFT) calculations suggest that the presence of cobalt vacancies increases the distance between the surface selenium atoms and the subsurface cobalt atoms. In addition, cobalt vacancies modify the electronic structure of the d-orbitals, lowering the energy barriers of the reaction and accelerating the reaction kinetics by improving the adsorption of the reactants. The research introduces a strategy for the rational design of efficient cathode materials in LOBs.