In this study, the electrochemical reduction of CO2 to CO within a bilayer cobalt phthalocyanine (CoPc)2 confinement system was systematically investigated using density functional theory (DFT). The results reveal that the (CoPc)2 architecture creates a well-defined catalytic microenvironment, in which the synergy between vertical spacing (regulated by moderate interlayer interactions) and lateral displacement gives rise to an optimal “Goldilocks zone”. This zone is characterized by a vertical distance (D) of 4.25–4.5 Å and a parallel displacement (L) of approximately 1 Å. Within this confined environment, the adsorption and desorption of key intermediates are optimally balanced, leading to enhanced catalytic activity. Electronic structure analysis further demonstrates that such spatial confinement induces asymmetric charge redistribution in the CO2 molecule, resulting in distinct regioselectivity. This work provides a general design strategy for developing high-performance and site-selective catalysts through precise engineering of interlayer geometric environments.
Yin et al. (2026) studied this question.