LAUSR

Despite the various strategies for achieving metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) with different microenvironments for electrochemical carbon dioxide reduction reaction (CO2RR), the synthesis-structure-performance correlation remains elusive due to the lack of well-controlled synthetic approaches. Here, we employed Ni nanoparticles as starting materials for the direct synthesis of nickel (Ni) SACs in one spot through harvesting the interaction between metallic Ni and N atoms in the precursor during the chemical vapor deposition growth of hierarchical N-doped graphene fibers. By combining with first-principle calculations, we found that the Ni-N configuration is closely correlated to the N contents in the precursor, in which the acetonitrile with a high N/C ratio favors the formation of Ni-N3, while the pyridine with a low N/C ratio is more likely to promote the evolution of Ni-N2. Moreover, we revealed that the presence of N favors the formation of H-terminated edge of sp2 carbon and consequently leads to the formation of graphene fibers consisting of vertically stacked graphene flakes, instead of the traditional growth of carbon nanotubes on Ni nanoparticles. With a high capability in balancing the *COOH formation and *CO desorption, the as-prepared hierarchical N-doped graphene nanofibers with Ni-N3 sites exhibit a superior CO2RR performance compared to that with Ni-N2 and Ni-N4 ones.