Constructing hierarchical nanosheet-on-microwire FeCo LDH@Co3O4 arrays for high-rate water oxidation

Alkaline electrochemical water oxidation powered by renewable energies is a promising and environmentally friendly way to produce hydrogen. The industrial water electrolyzers are commonly operated at a high current density, calling for abundant and durable active sites to participate in. The rational design of hierarchically structured electrocatalysts is thus essential to industrial water electrolyzers. Herein, we develop a Fe3+ induced nanosizing strategy for fabricating such a hierarchical FeCo LDH@Co3O4 (LDH: layered double hydroxide) nanostructure array for high-rate water oxidation. Density functional theory (DFT) simulations indicate that the introduction of Fe3+ with a small ion radius and high electrical repulsion in the LDH layer distorted the LDH layer, resulting in a reduced nanosheet size and enabling the formation of a hierarchical structure. Such structure cannot be achieved without the participation of Fe3+ cations. Benefiting from the significantly enhanced electrochemical surface areas and charge/mass transport due to the hierarchical structure together with the boosted intrinsic activity by electronic modulation of Fe3+, such FeCo LDH@Co3O4 electrode can deliver an industrial-level current density of 1,000 mA·cm−2 at a small overpotential of 392 mV for water oxidation. When assembled in a water electrolyzer, it delivers a current density of 100 mA·cm−2 at a low operation voltage of 1.61 V. Powered by solar light, the electrolyzer demonstrates high solar-to-hydrogen efficiency of 18.15% with stable and reproducible photoresponse. These results provide new insights for constructing hierarchical nanostructures for advanced water oxidation and other diverse applications.