The electrochemical conversion of low-concentration CO2 feedstock to value-added chemicals and fuels is a promising pathway for achieving direct valorization of waste gas streams. However, this is challenging due to significant competition from the hydrogen evolution reaction (HER) and lowered CO2 reduction (CO2R) kinetics as compared to systems that employ pure CO2. Here we show that terephthalic acid (TPA) functionalization can boost selectivity towards CO2R and suppress HER over a range of catalysts including Bi, Cu and Zn. For instance, TPA functionalized Bi attained a formate Faradaic efficiency (FEHCOO-) of 96.3 % at 300 mA cm-2 with pure CO2 feedstock. Density functional theory simulations indicate that this is because TPA functionalization modulates the binding energies of the key reaction intermediates *OCHO and *H. With low-concentration feedstock (15 % CO2) at 100 mA cm-2, we achieved a high FEHCOO- of 85.8 %, which was double that of an unmodified Bi catalyst. Using an electrolyzer with a porous solid electrolyte layer, we successfully showcase 30 h of continuous high-purity formic acid production with a 5 % CO2 feed. Taken together, our findings demonstrate that molecular tuning of a catalyst can be an effective strategy for enabling selective CO2R using low-concentration feedstock.
Keywords: CO2 reduction; Dilute Feedstock; Electrocatalysis; Electrochemistry; Organic Molecule.
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