Tandem electrocatalytic CO₂ reduction with Fe-porphyrins and Cu nanocubes enhances ethylene production

Copper-based tandem schemes have emerged as promising strategies to promote the formation of multi-carbon products in the electrocatalytic CO₂ reduction reaction. In such approaches, the CO-generating component of the tandem catalyst increases the local concentration of CO and thereby enhances the intrinsic carbon-carbon (C-C) coupling on copper. However, the optimal characteristics of the CO-generating catalyst for maximizing the C₂ production are currently unknown. In this work, we developed tunable tandem catalysts comprising iron porphyrin (Fe-Por), as the CO-generating component, and Cu nanocubes (Cucub) to understand how the turnover frequency for CO (TOF_CO) of the molecular catalysts impacts the C-C coupling on the Cu surface. First, we tuned the TOF_CO of the Fe-Por by varying the number of orbitals involved in the π-system. Then, we coupled these molecular catalysts with the Cu_cub and assessed the current densities and faradaic efficiencies. We discovered that all of the designed Fe-Por boost ethylene production. The most efficient Cu_cub/Fe-Por tandem catalyst was the one including the Fe-Por with the highest TOF_CO and exhibited a nearly 22-fold increase in the ethylene selectivity and 100 mV positive shift of the onset potential with respect to the pristine Cu_cub. These results reveal that coupling the TOF_CO tunability of molecular catalysts with copper nanocatalysts opens up new possibilities towards the development of Cu-based catalysts with enhanced selectivity for multi-carbon product generation at low overpotential.