Overcoming the Activity‐CH ₄ Reducibility Trade‐off in Dry Reforming of Methane via Spatially Separated Rh ₁ and Frustrated Lewis Pairs

Abstract Achieving high CO 2 conversion with minimal reductant input is essential for enabling a sustainable carbon cycle. Dry reforming of methane (DRM) represents a key pathway toward this goal, yet it is typically limited by CH 4 reducibility (moles of CO 2 consumed per mole of CH 4 ) of 1 mol CO2 mol CH4 −1 , and temperatures >700 °C. These limitations arise from an inherent trade‐off between catalytic activity and CH 4 reducibility, imposed by thermodynamic and kinetic constraints. Herein, we report a catalyst comprising spatially isolated Rh atoms (Rh 1 ) and frustrated Lewis pairs (FLPs) on porous CeO 2 nanorods, which decouples the DRM process into two elemental steps: CO 2 reduction and CH 4 partial oxidation. This spatial separation enables simultaneous high activity and exceptional CH 4 reducibility by facilitating *O migration form FLPs (for CO 2 reduction and *O storage) to Rh 1 (for CH 4 partial oxidation). The optimized catalyst exhibits a CO production rate of 83.4 mol g Rh −1 h −1 at 450 °C, surpassing state‐of‐the‐art catalysts, while achieving a CH 4 reducibility of 2.54 mol CO2 mol CH4 −1 , significantly exceeding the conventional DRM limit. Furthermore, the catalyst demonstrates outstanding stability over 350 h. This work offers a robust strategy for overcoming classical trade‐off in DRM, rendering it a promising candidate for industrial application.