Water splitting is an environmentally friendly strategy to produce hydrogen but is limited by the oxygen evolution reaction (OER). Therefore, there is an urgent need to develop highly efficient electrocatalysts. Here, NiFe layered double hydroxides (NiFe LDH) with tunable Ni/Fe composition exhibit corresponding dependent morphology, layered structure, and chemical states, leading to higher activity and better stability than that of conventional NiFe LDH‐based catalysts. The characterization data show that the low overpotentials (249 mV at 10 mA cm^–2), ultrasmall Tafel slopes (24 mV dec^–1), and high current densities of Ni₃Fe LDH result from the larger fraction of trivalent Fe³⁺ and the optimized local chemical environment with more oxygen coordination and ordered atomic structure for the metal site. Owing to the active intermediate species, Ni(Fe)OOH, under OER conditions and a reversible dynamic phase transition during the cycling process, the Ni₃Fe LDH achieves a high current density of over 2 A cm^–2 at 2.0 V, and durability of 400 h at 1 A cm^–2 in a single cell test. This work provides insights into the relationship between the composition, electronic structure of the layer, and electrocatalytic performance, and offers a scalable and efficient strategy for developing promising catalysts to support the development of the future hydrogen economy.

The cell performance and durability of polymer electrolyte membrane (PEM) water electrolyzers are limited by the surface passivation of titanium-based porous transport layers (PTLs). In order to ensure stable performance profiles over time, large amounts (≥1 mg·cm^–2) of noble metals (Au, Pt, Ir) are most widely used to coat titanium-based PTLs. However, their high cost is still a major obstacle toward commercialization and widespread application. In this paper, we assess different loadings of iridium, ranging from 0.005 to 0.05 mg·cm^–2 in titanium PTLs, that consequently affect the investment costs of PEM water electrolyzers. Concerning a reduction in the precious metal costs, we found that Ir as a protective layer with a loading of 0.025 mg·cm^–2 on the PTLs would be sufficient to achieve the same cell performance as PTLs with a higher Ir loading. This Ir loading is a 40-fold reduction over the Au or Pt loading typically used for protective layers in current commercial PEM water electrolyzers. We show that the Ir protective layer here not only decreases the Ohmic resistance significantly, which is the largest part of the gain in performance, but moreover, the oxygen evolution reaction activity of the iridium layer makes it promising as a cost-effective catalyst layer. Our work also confirms that the proper construction of a multifunctional interface between a membrane and a PTL indeed plays a crucial role in guaranteeing the superior performance and efficiency of electrochemical devices.