Molecular Templating Enables Precise CeNiC ₂ /Ni Heterostructures for Efficient Alkaline Hydrogen Oxidation

ABSTRACT The rational design and precise synthesis of highly efficient electrocatalysts for alkaline hydrogen oxidation reaction (HOR) are critical for anion exchange membrane fuel cells (AEMFCs) commercialization, yet they remain challenging. Here, we report a facile pyrolysis strategy employing Ce‐doped Ni‐based coordination polymers (CeNi‐CPs) as molecular templates to synthesize a series of bimetallic carbide‐based heterostructures (NiCeC 2 /Ni‐ x %). Subtle metal‐substitution within the CeNi‐CP template regulates atom ensembles, enabling the precise formation of a unique CeNiC 2 synergistic phase. Combined experimental and theoretical studies elucidate that the interfacial electron transfer from Ni to CeNiC 2 modulates the d ‐band of the heterostructure, optimizing intermediate binding energies. Coupled with a reduced water formation energy barrier, this effect contributes to excellent alkaline HOR performances. Notably, the CeNiC 2 /Ni‐1% catalyst achieves a high exchange density of 1.29 mA cm −2 disk , rivaling commercial Pt/C (20%) and representing a 3.7‐fold enhancement over pristine Ni. This work pioneers the atomically precise fabrication of heterostructured electrocatalysts driven by coordination chemistry and, for the first time, unlocks the significant potential of cerium‐nickel carbides for energy conversion applications.