Edge‐Rich Pt−O−Ce Sites in CeO2 Supported Patchy Atomic‐Layer Pt Enable a Non‐CO Pathway for Efficient Methanol Oxidation.

Rational design of efficient methanol oxidation reaction (MOR) catalyst that undergo non‐CO pathway is essential to resolve the long‐standing poisoning issue. However, it remains a huge challenge due to the rather difficulty in maximizing the non‐CO pathway by the selective coupling between the key *CHO and *OH intermediates. Here, we report a high‐performance electrocatalyst of patchy atomic‐layer Pt epitaxial growth on CeO2 nanocube (Pt ALs/CeO2) with maximum electronic metal‐support interaction for enhancing the coupling selectively. The small‐size monolayer material achieves an optimal geometrical distance between edge Pt−O−Ce sites and *OH absorbed on CeO2, which well restrains the dehydrogenation of *CHO, resulting in the non‐CO pathway. Meanwhile, the *CHO/*CO intermediate generated at inner Pt−O−Ce sites can migrate to edge, inducing the subsequent coupling reaction, thus avoiding poisoning while promoting reaction efficiency. Consequently, Pt ALs/CeO2 exhibits exceptionally catalytic stability with negligible degradation even under 1000 s pure CO poisoning operation and high mass activity (14.87 A/mgPt), enabling it one of the best‐performing alkali‐stable MOR catalysts. [ABSTRACT FROM AUTHOR]