Electronic Modification at Atomic Scale: Design and Preparation of Diatomic Structures by Atomic Layer Deposition for Methanol Steam Reforming

The electronic effects of bimetallic components in catalysis remain poorly understood. Herein, atomically dispersed transition metal (TM) modified platinum (Pt)‐based bimetallic catalysts were designed and synthesized with the atomic layer deposition (ALD) method. Methanol steam reforming (MSR) was selected as a probe reaction to investigate the atomic‐level electronic effects of nickel (Ni) and iron (Fe) on Pt species. In situ/ex situ characterizations, isotope labeling, and DFT calculations reveal that different transition metals and ALD cycles tune the Pt electronic structure, significantly affecting catalytic activity. Notably, the 10cNi/Pt1/CeO2 catalyst exhibits optimal electronic modification, achieving the highest MSR and water‐gas shift (WGS) conversions and the lowest activation energies. Additionally, kinetic isotope effect studies confirm that hydrogen formation proceeds via methanol dehydrogenation coupled with WGS. These findings provide new insights into electronic modifications at atomic scales within the bimetallic components, offering valuable guidance for the design and development of advanced catalytic systems.