Activating the Ni‐Contenting Carbon Nanotube by Covalent Triazine Frameworks to Form Atomically Dispersed Ni Sites with Curvature Effect for Electrocatalytic CO₂ Reduction

N‐coordinated Ni sites (NiNx) are effective catalysts for the electrochemical reduction of CO2 to CO. In most researches, modulating the coordination environment of Ni atoms is focused on to improve electrochemical CO2 reduction (ECR) performance. However, the influence of the carbon substrate's structure on the intrinsic activity of NiNx is seldom investigated. The highly curved surface of carbon nanotubes (CNT) may provide a unique curvature effect on NiNx. It is found that the Ni residues in CNT can be atomized to form NiNx sites on the surface of CNT (Ni‐N/CNT@covalent triazine framework [CTF]) through high‐temperature pyrolysis, using a soluble CTF nanosheet as N precursor. The π‐conjugated and ultrathin 2D structure of CTF enables closer interfacial contact between CTF and CNT, which avoids the formation of a thick carbon layer to maximize the curvature effect. Theoretical data reveal that the NiN3 configuration may act as a highly active ECR site, and the curvature effect from CNT can further tune the electronic structure of NiN3, thus improving the ECR kinetics. The Ni‐N/CNT@CTF‐based flow‐cell electrolyzer exhibits a jCO of 201 mA cm−2 at −0.9 V with a high FECO of 98%.