Synergistic electronic structure modulation in single-atomic Ni sites dispersed on Ni nanoparticles encapsulated in N-rich carbon nanotubes synthesized at low temperature for efficient CO2 electrolysis

Ni, N -doped carbon materials (Ni-N-C) are prosperous candidates for the electrochemical CO2 reduction reaction (CO2RR) due to their outstanding activity and selectivity. However, the role of the coexisting uncoordinated Ndoped sites and Ni nanoparticles (Ni-NPs) in overall CO2RR has been overlooked in prior studies. To address this gap, a low temperature synthesis method developed for Ni-NP-encapsulated Ni-N-C nanotube (Ni-NCNT) catalysts with atomically dispersed Ni-N4 and abundant uncoordinated N -doped sites, where Ni-NPs increase the electron density on Ni-N-C nanotube through carbon network and synergistically enhances the CO2RR activity. The systematic analysis reveals the cooperative role of Ni-NPs and uncoordinated N -doped sites in altering the electronic structure of Ni-N4 sites. The results of control experimental studies confirm the synergistic interaction of uncoordinated N -doped sites boost the CO2RR activity of Ni-N4 sites. Additionally, density functional theory calculations show that the strong interaction between the Ni-NPs and Ni-N-C did not affect the electronic structures of the Ni-N4 centers, but rather alter the electronic structure of uncoordinated pyridinic-N sites. This variation led to decreased the energy barriers of rate -limiting steps of COOH* formation on Ni-N4 and N -doped sites, resulting in excellent CO2RR performance.