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In this work, defect-rich ordered mesoporous spinel oxides, including CoCo2O4, NiCo2O4, and ZnCo2O4, were developed as bifunctional electrocatalysts toward oxygen reduction and evolution reactions (ORR and OER, respectively). The materials are synthesized via nanocasting and modified by chemical treatment with 0.1 M NaBH4 solution to enhance the defect concentration. The synthesized samples have metal and oxygen divacancies (VCo + VO) as the primary defect sites, as indicated by positron annihilation lifetime spectroscopy (PALS). Cation s