In this work, a novel single-atom alloy electrocatalyst (SAAE) was developed for enhanced electrocatalysis in next-generation energy technologies. The catalyst, composed of single-atom Rh and bulk Ni on FeV3O8 support, overcomes challenges related to stability and efficiency in electrochemical reactions. The work function difference between Rh and Ni, as confirmed by computational and synchrotron-based analysis, facilitates superior electric polarization and ohmic contact with FeV3O8. The FeV3O8@RhNi demonstrates outstanding performance in oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs), with high half-wave potential (0.90 V) and low overpotential (120 mV at 10 mA cm−2). In zinc-air batteries, it maintains a stable discharge–charge voltage gap, specific capacity of 810 mAh·g−1, peak power density of 186 mW·cm−2 at 320 mA·cm−2, and cycle stabilities exceeding 859 h at 10 mA·cm−2. The catalyst also proves its durability in flexible zinc–air batteries, indicating its potential for efficient electrocatalytic reactions in emerging energy technologies.

The integration of bifunctionally active sites of multielement random alloy catalysts with other metal oxide electrocatalysts is a promising strategy for efficient electrochemical reactions. In this study, a novel combination of virtual crystal approximation and hydrothermal synthesis was used to investigate the composition-dependent structure and electrical property in a Ag1−xNix catalyst. The combination showed that a hexagonal closed-packed structure of Ag1−xNix with a compositional ratio of 6:4 (Ag:Ni) had electrical conductivity of ∼2 × 107 S∙cm−1 and an ionization potential of − 5.4 eV. Furthermore, the bifunctional oxygen electrocatalytic efficiencies of Ag0.6Ni0.4 were improved by forming a heterointerface with the CoNb2O6 electrocatalyst, resulting in a discharge-charge voltage gap of 0.81 V over 587 h, peak power density of 178.9 mW∙cm−2, and specific capacity of 806.8 mA∙h∙g−1 in a zinc–air battery. This approach was applied to pouch-type zinc–air batteries, resulting in long-term stability of over 158.6 h at 10 mA∙cm−2.