The Significance of the ′Insignificant′: Non‐covalent Interactions in CO2 Reduction Reactions with 3C‐TM (TM=Sc‐Zn) Single‐Atom Catalysts

Abstract With energy shortages and excessive CO 2 emissions driving climate change, converting CO 2 into high‐value‐added products offers a promising solution for carbon recycling. We investigate CO 2 reduction reactions (CO 2 RR) catalyzed by 10 single‐atom catalysts (SACs), incorporating weak non‐covalent interactions, specifically lone pair‐π and H‐π interactions. The SACs, consisting of transition metals coordinated by three carbon atoms in a defective graphene substrate (3C‐TM, TM=Sc‐Zn), leverage these interactions to influence the energy fluctuations of intermediates and the limiting potentials of CO 2 RR, without altering the overall reaction pathway. Our findings show that SACs based on early transition metals (Sc, Ti, V, Cr) can serve as catalysts for C 1 products, including HCOOH, HCHO, CH 3 OH, and CH 4 , while those based on Fe and Co are suitable for CO formation. Driving force analysis helps bridge theoretical results with experimental observations and propose a modified approach for assessing hydrogen evolution reactions (HER) competition. SACs based on Ni and Cu exhibit moderate HER tolerance, while early transition metals excel in selective CO 2 reduction. We also identify a linear scaling relationship between the free energies of *COOH and *CO. This study offers valuable insights for future experimental studies and large‐scale computational screenings.