Embedding Reverse Electron Transfer Between Stably Bare Cu Nanoparticles and Cation‐Vacancy CuWO4

Abstract Cu nanoparticles (NPs) have attracted widespread attention in electronics, energy, and catalysis. However, conventionally synthesized Cu NPs face some challenges such as surface passivation and agglomeration in applications, which impairs their functionalities in the physicochemical properties. Here, the issues above by engineering an embedded interface of stably bare Cu NPs on the cation‐vacancy CuWO 4 support is addressed, which induces the strong metal‐support interactions and reverse electron transfer. Various atomic‐scale analyses directly demonstrate the unique electronic structure of the embedded Cu NPs with negative charge and anion oxygen protective layer, which mitigates the typical degradation pathways such as oxidation in ambient air, high‐temperature agglomeration, and CO poisoning adsorption. Kinetics and in situ spectroscopic studies unveil that the embedded electron‐enriched Cu NPs follow the typical Eley‐Rideal mechanism in CO oxidation, contrasting the Langmuir‐Hinshelwood mechanism on the traditional Cu NPs. This mechanistic shift is driven by the Coulombic repulsion in anion oxygen layer, enabling its direct reaction with gaseous CO to form the easily desorbed monodentate carbonate.