High-entropy alloy aerogels promote selective glycerol oxidation to tartronate at industrial current densities

The highly selective electrosynthesis of tartronate (TA) from glycerol oxidation reaction (GOR) at industrial current densities remains a grand challenge, as it necessitates the concurrent oxidation of two primary hydroxyl groups while suppressing C-C cleavage. Herein, we engineer a PtCuCoCeSn high-entropy alloy aerogel electrocatalyst for efficient glycerol-to-TA electrooxidation under industrially relevant conditions. This catalyst delivers a high current density of 461 mA cm−2 at 1.0 VRHE, alongside a TA selectivity of 81.4%. In situ characterization and theoretical calculations reveal that Ce modulates the glycerol adsorption conformation, enhances the adsorption of glycerate intermediates, and promotes its conversion to TA. Meanwhile, Sn facilitates TA desorption and suppresses the C-C cleavage, thereby ensuring high selectivity at elevated current. Furthermore, in a membrane electrode assembly (MEA) electrolyzer configured with Pt1.5CuCoCeSn | | PtCuCoCeSn, the system achieves a stable TA selectivity of 78.9% at a cell voltage of 1.6 V with a TA production rate of 4.9 mmol h−1, and maintains stable operation for over 240 h. This work provides fundamental insights into the design of high-entropy alloys for the sustainable electrosynthesis of value-added chemicals at scale. The production of tartronate from glycerol electrooxidation is limited by low selectivity at industrial-scale current densities. Here, the authors report a PtCuCoCeSn high-entropy alloy aerogel for regulated glycerol adsorption, enabling 81.4% selectivity and stable operation up to 240 hours.