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

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. © 2022 Wiley-VCH GmbH.