Entanglement of Spatial and Energy Segmentation for C₁ Pathways in CO₂ Reduction on Carbon Skeleton Supported Atomic Catalysts

Abstract Electroreduction of CO₂ has become the most attractive approach to generate value‐added chemicals and fuels. Products of single atomic catalysts (SAC) in CO₂ reduction reaction reactions (CO₂RR) are mostly limited to CO since the contributions of spatial and thermodynamic factors are not distinguished. To break through the challenges, comprehensive explorations in graphdiyne(GDY)‐based SAC are made, to reveal detailed influences of active sites, elements, and adsorptions on the selectivity and reaction energy of the C₁ pathway. Unique d electrons dominated adsorption behaviors are identified, where the d⁶ boundary is able to help screen out promising candidates for achieving complicated C₂₊ products. Based on spatial and thermodynamic factors, metal sites are still the most promising active sites. The transition metal based GDY‐SACs show element‐dependent electroactivity towards different products in CO₂RR. Meanwhile, the GDY‐Pr and GDY‐Pm SACs are promising candidates for the CO₂RR and even C₂ products in the future. This work supplies in‐depth insights into the CO₂RR to facilitate the design of efficient atomic catalysts in future work.