Precursor-mediated in situ growth of hierarchical N-doped graphene nanofibers confining nickel single atoms for CO₂ electroreduction.

Abstract

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.