Aromatic Ester-Functionalized Ionic Liquid for Highly Efficient CO2 Electrochemical Reduction to Oxalic Acid.

Electrochemical reduction of CO2 into valuable chemicals is a significant route to utilize CO2 resources. Among various electroreduction products, oxalic acid (H2 C2 O4 ) is an important chemical for pharmaceuticals, rare earth extraction, and metal processing. Here, an aprotic aromatic ester-functionalized ionic liquid (IL), 4-(methoxycarbonyl) phenol tetraethylammonium ([TEA][4-MF-PhO]), was designed as an electrolyte for CO2 electroreduction into oxalic acid. It exhibited a large oxalic acid partial current density of 9.03 mA cm-2 with a faradaic efficiency (FE) of 86 % at -2.6 V (vs. Ag/Ag+ ), and the oxalic acid formation rate was as high as 168.4 μmol cm-2  h-1 , which is the highest reported value to date. Moreover, the results of density functional theory calculations demonstrated that CO2 was efficiently activated to a -COOH intermediate by bis-active sites of the aromatic ester anion via the formation of a [4-MF-PhO-COOH]- adduct, which finally dimerized into oxalic acid.