UC Berkeley

Microenvironments tailored by multifunctional secondary coordination sphere groups can enhance catalytic performance at primary metal active sites in natural systems. Here, we capture this biological concept in synthetic systems by developing a family of iron porphyrins decorated with imidazolium (im) pendants for the electrochemical CO₂ reduction reaction (CO₂ RR), which promotes multiple synergistic effects to enhance CO₂ RR and enables the disentangling of second-sphere contributions that stem from each type of interaction. Fe-ortho-im(H), which poises imidazolium units featuring both positive charge and hydrogen-bond capabilities proximal to the active iron center, increases CO₂ binding affinity by 25-fold and CO₂ RR activity by 2000-fold relative to the parent Fe tetraphenylporphyrin (Fe-TPP). Comparison with monofunctional analogs reveals that through-space charge effects have a greater impact on catalytic CO₂ RR performance compared to hydrogen bonding in this context.