Nature determines selectivity and activity in biological reactive centers, based on single metal atom macrocycles, by properly tuning the primary coordination sphere and the surrounding protein scaffold. In a biomimetic approach, we show that activation of carbon dioxide at a 2D crystal of phthalocyanines supported by graphene can be controlled by chemical tuning of the position of the Dirac cones of the support through oxygen adsorption. The room temperature stabilization of the CO2−Fe chemical bond, detected in situ and confirmed by computational density-functional theory simulations, is obtained by governing the charge transfer across the graphene−metallorganic layer interface upon oxidation of graphene at close-to-ambient conditions. In this way, we can turn a weakly binding site into a strong one in an artificial structure that mimics many features of complex biological systems.
