Core‐Shell Structure of Ni₁₇W₃@W Induced High Intrinsic Activity and Stability for Alkaline Hydrogen Oxidation

Abstract Hydrogen energy has attracted considerable attention due to its zero emissions and high conversion efficiency. However, the sluggish anodic kinetics in anion exchange membrane fuel cells (AEMFCs) necessitate the use of high‐load platinum‐group metal (PGM) catalysts, significantly increasing system cost. Herein, a nickel‐based electrocatalyst of Ni₁₇W₃@W with a unique core‐shell structure is reported, which exhibits outstanding intrinsic activity with an electrochemical surface area‐normalized exchange current density of 0.072 mA cm_Ni⁻². Compared to commercial Pt/C, Ni₁₇W₃@W also demonstrates superior CO tolerance and long‐term operational stability. X‐ray absorption spectroscopy and ultraviolet photoelectron spectroscopy reveal an increased valence state of Ni in Ni₁₇W₃@W, leading to a downshift of d‐band center and a corresponding decrease in hydrogen binding energy. In situ surface enhanced infrared absorption spectroscopy confirms that the W shell optimizes the interfacial water structure, enhancing the hydrogen‐bonding network and further promoting the hydrogen oxidation reaction. Moreover, the porous W shell serves as a protective barrier, effectively preventing oxidation of the Ni₁₇W₃ core and ensuring long‐term catalyst durability. This work offers valuable insights for the rational design of high‐performance non‐PGM anode catalysts in AEMFCs.