Preserving Molecular Tuning for Enhanced Electrocatalytic CO₂-to-Ethanol Conversion

Modifying catalyst surface with small molecular-additives presents a promising avenue for enhancing electrocatalytic performance. However, challenges arise in preserving the molecular-additives and maximizing their tuning effect, particularly at high current densities. Herein, we develop an effective strategy to preserve the molecular-additives on electrode surface by applying a thin protective layer. Taking 4-dimethylaminopyridine (DMAP) as an example of a molecular-additive, the hydrophobic protection layer on top of the DMAP-functionalized Cu-catalyst effectively prevents its leaching during CO₂ electroreduction (CO₂R). Consequently, the confined DMAP molecules substantially promote the CO₂-to-multicarbon conversion at low overpotentials. For instance, at a potential as low as -0.47 V vs. reversible hydrogen electrode, the DMAP-functionalized Cu exhibits over 80 % selectivity towards multi-carbon products, while the pristine Cu shows only ~35 % selectivity for multi-carbon products. Notably, ethanol appears as the primary product on DMAP-functionalized Cu, with selectivity approaching 50 % at a high current density of 400 mA cm^-2. Detailed kinetic analysis, in situ spectroscopies, and theoretical calculations indicate that DMAP-induced electron accumulations on surface Cu-sites decrease the reaction energy for C-C coupling. Additionally, the interactions between DMAP and oxygenated intermediates facilitate the ethanol formation pathway in CO₂R. Overall, this study showcases an effective strategy to guide future endeavors involving molecular tuning effects.