Electrocatalytic hydrogenation (ECH) of oxalic acid (OX) to produce glycolic acid (GA), an important building block of biodegradable polymers as well as application in various branches of chemistry, has attracted extensive attention in the industry, while it still encounters challenges of low reaction rate and selectivity. Herein, we reported a cation adsorption strategy to realize the efficient ECH of OX to GA by adsorbing Al3+ ions on an anatase titanium dioxide (TiO2) nanosheet array, achieving 2-fold enhanced GA productivity (1.3 vs 0.65 mmol cm-2 h-1) with higher Faradaic efficiency (FE) (85 vs 69%) at -0.74 V vs RHE. We reveal that the Al3+ adatoms on TiO2 both act as electrophilic adsorption sites to enhance the carbonyl (C═O) adsorption of OX and glyoxylic acid (intermediate) and also promote the generation of reactive hydrogen (H*) on TiO2, thus promoting the reaction rate. This strategy is demonstrated effective for different carboxylic acids. Furthermore, we realized the coproduction of GA at the bipolar of a H-type cell by pairing ECH of OX (at cathode) and electrooxidation of ethylene glycol (at anode), demonstrating an economical manner with maximum electron economy.
Keywords: anatase TiO2 nanosheet array; electrocatalytic hydrogenation; glycolic acid; oxalic acid; reactive hydrogen species.