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The development of facile strategies to tune the oxygen vacancy (OV) content in transition metal oxides (TMOs) is paramount to obtain low-cost and stable electrocatalysts, but still highly challenging. Taking NiCo2O4 as a model system, we have experimentally established a facile calcination and electrochemical activation (EA) methodology to dramatically increase the concentration of OVs and provide theoretical insight into how the concentration of OVs affects the performance of spinel TMOs towards the electrochemical hydrogen evolution reaction (HER). A self-supported cathode of OV-rich NiCo2O4 nanowire arrays was found to exhibit higher HER activity and better stability in alkaline media than its counterparts with fewer OVs. The electrocatalytic HER activity was in good agreement with the increasing concentration of OVs in the studied samples. A large current density of 360 mA·cm–2 was reached with an overpotential of only 317 mV. Additionally, such a facile strategy was able to efficiently generate OVs in other TMOs (e.g., CoFe2O4 and NiFe2O4) for enhanced HER performance. In addition, our theoretical results suggest that the increasing OV concentration reduces the adsorption energy of water molecules and their dissociation energy barrier on the surface of the catalyst, thus leading to performance improvement of spinel TMOs toward the electrochemical HER. This work may open a new avenue to increase the concentration of OVs in TMOs in a controlled manner for promising applications in a variety of fields.
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