Synergistic Activation of Inert Iron Oxide Basal Planes through Heterostructure Formation and Doping for Efficient Hydrogen Evolution

Abstract Iron oxides have emerged as a very promising and cost‐effective alternative to precious metal catalysts for hydrogen production. However, the inert basal plane of iron oxides needs to be activated to enhance their catalytic efficiency. In this study, we employed heterostructure engineering and doped nickel to cooperatively activate the basal planes of iron oxide (Ni−Fe 2 O 3 /CeO 2 HSs) to achieve high hydrogen evolution reaction (HER) activity. The Ni−Fe 2 O 3 /CeO 2 HSs electrocatalyst demonstrates excellent basic HER activity and stability, such as an extremely low overpotential of 43 mV at 10 mA cm −2 current density and corresponding Tafel slope of 58.6 mV dec −1 . The increase in electrocatalyst activity and acceleration of hydrogen precipitation kinetics arises from the dual modulation of Ni doping and heterostructure, which not only modulates the electrocatalyst‘s electronic structure, but also increases the number and exposure of active sites. Remarkably, the generation of heterogeneous structure makes the catalyst se. The Ni‐doped catalyst has not only increased HER activity but also low‐temperature resistance. These results suggest that the synergistic activation of inert iron oxide basal planes through heterostructure formation and doping is a feasible strategy. Furthermore, for efficient electrocatalytic water splitting, this technique can be extended to other non‐noble metal oxides.