Step‐Associated Cu‐Ceria Interfaces Enhance Catalytic Activity and Selectivity

ABSTRACT Precise control of metal–support interactions is essential for understanding and steering catalytic processes. Here, we demonstrate that the surface location of metal nanoparticles (NPs) on oxide supports can strongly influence catalytic performance. Using atom‐trapped Cu catalysts as precursors enabled the formation of Cu NPs with distinct Cu–CeO 2 interfacial environments compared with catalysts prepared by impregnation or colloidal methods. These resulting catalysts exhibit enhanced CO 2 hydrogenation toward methanol formation by promoting formate activation. Enhanced reactivity arises from these Cu–CeO 2 interfacial environments that render the methanol formation pathway thermodynamically more favorable, as revealed by theoretical calculations. These findings provide mechanistic insights into how NP anchoring environments influence catalytic activity and selectivity, offering a rational design strategy for oxide‐supported metal catalysts.