D‐Orbital Coupling and Intrinsic Strain Engineering in Single Atom Tailored Ternary Nanoalloys for Enhanced Methanol Electro‐Oxidation

Methanol oxidation reaction (MOR) is an essential anode reaction in direct methanol fuel cells (DMFCs). However, current catalysts often suffer from low activity, poor stability, and CO poisoning. Here, a single‐atom‐tailored ternary alloy, PdCoNi/Cr‐SAC, distinguished by single‐atom‐induced strain, was successfully fabricated. The resulting catalyst delivered a high specific activity of 49.32 mA cm −2 , representing 9.2‐fold enhancements over Pd/C. Theoretical calculations and experimental analysis unveil that the outstanding MOR activity of PdCoNi/Cr‐SAC is ascribed to the SAC‐tailored nanoalloy configuration, which induce a downward shift in the d‐band center, strong d‐orbital coupling, weakened CO binding, and reduced MOR energy barrier. In situ surface‐enhanced Raman spectroscopy (SERS) and attenuated total reflectance surface‐enhanced infrared spectroscopy (ATR‐SEIS) verified the PdCoNi/Cr‐SAC promotes a CO‐free MOR pathway with enhanced hydroxyl‐groups formation. This study progresses the design of single‐atom‐tailored ternary nanoalloy with intrinsic strain, opening a promising route for the development of CO‐tolerance MOR electrocatalysts.