Iridium–Tungsten Alloy Nanodendrites as pH-Universal Water-Splitting Electrocatalysts

[Image: see text] The development of highly efficient and durable electrocatalysts for high-performance overall water-splitting devices is crucial for clean energy conversion. However, the existing electrocatalysts still suffer from low catalytic efficiency, and need a large overpotential to drive the overall water-splitting reactions. Herein, we report an iridium–tungsten alloy with nanodendritic structure (IrW ND) as a new class of high-performance and pH-universal bifunctional electrocatalysts for hydrogen and oxygen evolution catalysis. The IrW ND catalyst presents a hydrogen generation rate ∼2 times higher than that of the commercial Pt/C catalyst in both acid and alkaline media, which is among the most active hydrogen evolution reaction (HER) catalysts yet reported. The density functional theory (DFT) calculations reveal that the high HER intrinsic catalytic activity results from the suitable hydrogen and hydroxyl binding energies, which can accelerate the rate-determining step of the HER in acid and alkaline media. Moreover, the IrW NDs show superb oxygen evolution reaction (OER) activity and much improved stability over Ir. The theoretical calculation demonstrates that alloying Ir metal with W can stabilize the formed active iridium oxide during the OER process and lower the binding energy of reaction intermediates, thus improving the Ir corrosion resistance and OER kinetics. Furthermore, the overall water-splitting devices driven by IrW NDs can work in a wide pH range and achieve a current density of 10 mA cm(–2) in acid electrolyte at a low potential of 1.48 V.