Rational design of single atom catalyst is critical for efficient sustainable energy conversion. However, the atomic-level control of active sites is essential for electrocatalytic materials in alkaline electrolyte. Moreover, well-defined surface structures lead to in-depth understanding of catalytic mechanisms. Herein, we report a single-atomic-site ruthenium stabilized on defective nickel-iron layered double hydroxide nanosheets (Ru₁/D-NiFe LDH). Under precise regulation of local coordination environments of catalytically active sites and the existence of the defects, Ru₁/D-NiFe LDH delivers an ultralow overpotential of 18 mV at 10 mA cm⁻² for hydrogen evolution reaction, surpassing the commercial Pt/C catalyst. Density functional theory calculations reveal that Ru₁/D-NiFe LDH optimizes the adsorption energies of intermediates for hydrogen evolution reaction and promotes the O–O coupling at a Ru–O active site for oxygen evolution reaction. The Ru₁/D-NiFe LDH as an ideal model reveals superior water splitting performance with potential for the development of promising water-alkali electrocatalysts.

Rational design of the catalysts is impressive for sustainable energy conversion. However, there is a grand challenge to engineer active sites at the interface. Herein, hierarchical transition bimetal oxides/sulfides heterostructure arrays interacting two-dimensional MoO_x/MoS₂ nanosheets attached to one-dimensional NiO_x/Ni₃S₂ nanorods were fabricated by oxidation/hydrogenation-induced surface reconfiguration strategy. The NiMoO_x/NiMoS heterostructure array exhibits the overpotentials of 38 mV for hydrogen evolution and 186 mV for oxygen evolution at 10 mA cm⁻², even surviving at a large current density of 500 mA cm⁻² with long-term stability. Due to optimized adsorption energies and accelerated water splitting kinetics by theory calculations, the assembled two-electrode cell delivers the industrially relevant current densities of 500 and 1000 mA cm⁻² at record low cell voltages of 1.60 and 1.66 V with excellent durability. This research provides a promising avenue to enhance the electrocatalytic performance of the catalysts by engineering interfacial active sites toward large-scale water splitting.

Rational design efficient transition metal-based electrocatalysts for oxygen evolution reaction (OER) is critical for water splitting. However, industrial water-alkali electrolysis requires large current densities at low overpotentials, always limited by intrinsic activity. Herein, we report hierarchical bimetal nitride/hydroxide (NiMoN/NiFe LDH) array as model catalyst, regulating the electronic states and tracking the relationship of structure-activity. As-activated NiMoN/NiFe LDH exhibits the industrially required current density of 1000 mA cm⁻²at overpotential of 266 mV with 250 h stability for OER. Especially, in-situ electrochemical spectroscopic reveals that heterointerface facilitates dynamic structure evolution to optimize electronic structure. Operando electrochemical impedance spectroscopy implies accelerated OER kinetics and intermediate evolution due to fast charge transport. The OER mechanism is revealed by the combination of theoretical and experimental studies, indicating as-activated NiMoN/NiFe LDH follows lattice oxygen oxidation mechanism with accelerated kinetics. This work paves an avenue to develop efficient catalysts for industrial water electrolysis via tuning electronic states.