Monolayer NiIr-Layered Double Hydroxide as a Long-Lived Efficient Oxygen Evolution Catalyst for Seawater Splitting.

Promoting the oxygen evolution reaction (OER) with saline water is highly desired to realize seawater splitting. This requires OER catalysts to resist serious corrosion and undesirable chloride oxidation. We introduce a 5d transition metal, Ir, to develop a monolayer NiIr-layered double hydroxide (NiIr-LDH) as the catalyst with enhanced OER performance for seawater splitting. The NiIr-LDH catalyst delivers 500 mA/cm at only 361 mV overpotential with ∼99% O Faradaic efficiency in alkaline seawater, which is more active than commercial IrO (763 mV, 23%) and the best known OER catalyst NiFe-LDH (530 mV, 92%). Moreover, it shows negligible activity loss at up to 650 h chronopotentiometry measurements at an industrial level (500 mA/cm), while commercial IrO and NiFe-LDH rapidly deactivated within 0.2 and 10 h, respectively. The incorporation of Ir into the Ni(OH) layer greatly altered the electron density of Ir and Ni sites, which was revealed by X-ray absorption fine structure and density functional theory (DFT) calculations. Coupling the electrochemical measurements and in situ Raman spectrum with DFT calculations, we further confirm that the generation of rate-limiting intermediate *O and *OOH species was accelerated on Ni and Ir sites, respectively, which is responsible for the high seawater splitting performance. Our results also provide an opportunity to fabricate LDH materials containing 5d metals for applications beyond seawater splitting.