Carbon-Supported Dual-Nickel Atom Catalysts With Stabilized Ni─N₃ Active Sites for Efficient CO₂ Electroreduction

Abstract

Unsaturated Ni─N₃ single-atom catalysts (SACs) have been explored to overcome the conventional Ni─N₄ structural limitations for electrochemical CO₂ reduction reaction (eCO₂RR). However, their inherently low structural stability has significantly hindered practical applications. Herein, we developed dual-nickel atom catalysts (Ni-DACs) to stabilize unsaturated Ni─N₃ atomic sites by constructing N₃Ni─NiN₃ dual-atom structures (Ni₂─N₆ sites) from coal. Theoretical prediction reveals that Ni₂─N₆ sites exhibit lower energy barriers for *COOH intermediate generation relative to Ni─N₄ sites and reduce the *CO desorption barriers compared to Ni₃─N₆ sites, thereby boosting reaction kinetics for CO generation. Aberration-corrected scanning transmission electron microscopy and synchrotron X-ray absorption fine structure spectroscopy validate the atomic dispersion of Ni dual-atom sites. The prepared Ni-DACs sample achieves the highest Faradaic efficiency for CO (FE_CO) generation of 98.6% at −0.8 V vs. reversible hydrogen electrode (RHE) and maintains a high FE_CO over 94% from −0.8 to −1.2 V vs. RHE. It also shows a superior CO production turnover frequency as high as 7885 h⁻¹ even at 1.19 V overpotential, outperforming Ni-SACs (2615 h⁻¹). This study offers a scalable approach for stabilizing unsaturated Ni─N₃ SACs to forge a path for their application in eCO₂RR.

Keywords

CO₂ electroreduction / coal / dual-nickel atom catalysts / intermediate adsorption / NiN₃ sites

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