In Situ Exsolution of Ba₃(VO₄)₂ Nanoparticles on a V-Doped BaCoO_3-δ Perovskite Oxide with Enhanced Activity for...

The successful preparation of a perovskite-based heterostructure is important for broadening the applications of perovskites in the field of electrocatalysis, especially in a hydrogen evolution reaction (HER). Nevertheless, the limited active sites of perovskites severely hindered the HER properties. Herein, an in situ exsolution method was used to construct a nanocomposite based on V-doped BaCoO_3-δ decorated with Ba₃(VO₄)₂ (BVCO19) for alkaline HER. The exsolved Ba₃(VO₄)₂ can induce more Co⁴⁺ ions on BaCoO_3-δ, which serves as active sites for the release of H₂. Meanwhile, by regulating the valency of V and Co species, the catalyst can reach a charge balance by generating more oxygen vacancies, which greatly facilitates the adsorption and dissociation of H₂O molecules. The synergistic effect between the oxygen vacancies and high-valence Co⁴⁺ leads to an enhanced HER performance of BVCO19. The as-obtained catalyst delivers a low overpotential of 194 mV at 10 mA cm^-2 as well as impressive stability for 100 h in alkaline media, which outperforms pristine BaCoO_3-δ and most of the nonprecious-based perovskite oxides. This work provides new insights into the preparation of perovskite-based heterostructure for boosting HER.