Generating high-energy compounds with heteroatomic bonds via electrochemical reactions has attracted interest owing to the highly desired goal of achieving a net zero carbon state. In this dimension, herein, heteroatomic compounds, such as acetamide (CH3CONH2), were successfully produced together with the formation of ethylene glycol and other C2+ compounds by integrating CO2RR with nitrate reduction reaction (NtRR). Highly porous nickel nanodendrites (p-Ni NDs) with a porifera architecture were constructed via the electrodeposition method and subsequent etching process. In 0.05 M KNO3 and 0.5 M KHCO3 electrolyte, p-Ni NDs generated acetamide and ethylene glycol at the yield rate of 657 μg h−1 cm−2 and 640 μg h−1 cm−2 with an FE of 23.2% and 18.0% under an applied voltage of −0.3 V vs. RHE, respectively. 1H NMR spectroscopy was extensively used to detect and quantify the products. During the reaction, the surface of p-Ni NDs remained in the metallic state, which was confirmed by several X-ray spectroscopic techniques. Density functional theory (DFT) calculations revealed that *COHCOH(a) is the crucial intermediate in the production of acetamide. Both the experimental and theoretical experiments substantiated the high activity of p-Ni NDs towards acetamide formation via C-N coupling.
