Strong Heteroatomic Bond‐Induced Confined Restructuring on Ir−Mn Intermetallics Enable Robust PEM Water Electrolyzers

Low-iridium acid-stabilized electrocatalysts for efficient oxygen evolution reaction (OER) are crucial for the market deployment of proton exchange membrane (PEM) water electrolysis. Manipulating the in situ reconstruction of Ir-based catalysts with favorable kinetics is highly desirable but remains elusive. Herein, we propose an atomic ordering strategy to modulate the dynamic surface restructuring of catalysts to break the activity/stability trade-off. Under working conditions, the strong heteroatom-bonded structure triggers rational surface-confined reconstruction to form self-stabilizing amorphous (oxy)hydroxides on the model Ir-Mn intermetallic (IMC). Combined in situ/ex situ characterizations and theoretical analysis demonstrate that the induced strong covalent Ir-O-Mn units in the catalytic layer weaken the formation barrier of OOH* and promote the preferential dynamic replenishment/conversion pathway of H₂O molecules to suppress the uncontrollable participation of lattice oxygen (about 2.6 times lower than that of pure Ir). Thus, a PEM cell with Ir-Mn IMC as anode "pre-electrocatalyst" (0.24 mg_Ir cm^-2) delivers an impressive performance (3.0 A cm^-2@1.851 V@80 °C) and runs stably at 2.0 A cm^-2 for more than 2,000 h with the cost of USD 0.98 per kg H₂, further validating its promising application. This work highlights surface-confined evolution triggered by strong heteroatom bonds, providing insights into the design of catalysts involving surface reconstruction.