Molecular Solvation Environment Controls the Active Site in Cation-Mediated Electrocatalytic CO2 Reduction to Methanol

Electrocatalytic synthesis of higher-value products from waste molecules is an emerging technique for sustainable chemical catalysis. Heterogeneous molecular electrocatalysts are an important group of materials where the catalytic activity and selectivity can be controlled using molecularly defined active sites. Despite extensive efforts to synthesize better molecular catalysts, the effects of molecular aggregation, which dominates the interaction of the catalyst with the electrode surface as well as with the electrochemical solvation environment, are not fully understood. Using cobalt phthalocyanine (CoPc) dispersed on carbon nanotubes (CNTs) as a model system, we find that controlling the direct interaction of the molecular catalyst with cations in the electrochemical double layer (EDL) results in significantly enhanced performance for CO 2 reduction (CO 2 RR). Specifically, molecular dispersion of the CoPc onto CNTs yields a 4-fold increase in total current density and 8-fold increase in methanol (MeOH) selectivity compared to aggregated CoPc physically mixed with the same CNT support, enabling CO 2 to MeOH conversion with 42.34% Faradaic efficiency (FE). Using surface-selective sum-frequency generation (SFG) vibrational spectroscopy, direct detection of reaction intermediates reveals that the potential-dependent adsorption of two distinct CO intermediates at two types of active sites, one less active and producing mostly CO, the other more active and able to produce methanol. DFT calculations show that the CO intermediate responsible for selective MeOH production results from the direct interaction with cations present in the EDL. This interaction, which is only possible when CoPc is molecularly dispersed on the electrode surface, is responsible for the cation-assisted conversion of CO to MeOH. Control experiments using either strongly hydrated Li + , or chelated K + by 18-crown-6-ether, which suppress MeOH formation, further confirms the important role of this interaction. Similarly significant enhancement effects are also observed for nitrate reduction reaction (NO 3 RR) and oxygen reduction reaction (ORR), showing that dispersing molecular catalysts into monomers states is a general design parameter required to enhance activity and selectivity by cation-assisted reaction kinetics inside the EDL.