Generating Multi-Carbon Products by Electrochemical CO₂ Reduction via Catalytically Harmonious Ni/Cu Dual Active Sites

Despite the unique advantages of single-atom catalysts, molecular dual-active sites facilitate the C-C coupling reaction for C₂ products toward the CO₂ reduction reaction (CO₂RR). The Ni/Cu proximal dual-active site catalyst (Ni/Cu-PASC) is developed, which is a harmonic catalyst with dual-active sites, by simply mixing commercial Ni-phthalocyanine (Ni-Pc) and Cu-phthalocyanine (Cu-Pc) molecules physically. According to scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM) energy dispersive spectroscopy (EDS) data, Ni and Cu atoms are separated, creating dual-active sites for the CO₂RR. The Ni/Cu-PASC generates ethanol with an FE of 55%. Conversely, Ni-Pc and Cu-Pc have only detected single-carbon products like CO and HCOO^-. In situ X-ray absorption spectroscopy (XAS) indicates that CO generation is caused by the stable Ni active site's balanced electronic state. The CO production from Ni-Pc consistently increased the CO concentration over Cu sites attributed to subsequent reduction reaction through a C-C coupling on nearby Cu. The CO bound (HCOO^-) peak, which can be found on Cu-Pc, vanishes on Ni/Cu-PASC, as shown by in situ fourier transformation infrared (FTIR). The characteristic intermediate of *CHO instead of HCOO^- proves to be the prerequisite for multi-carbon products by electrochemical CO₂RR. The work demonstrates that the harmonic dual-active sites in Ni/Cu-PASC can be readily available by the cascading proximal active Ni- and Cu-Pc sites.