High‐Selectivity Electrocatalytic Oxidation of Glycerol to C3‐Glyceraldehyde Coupled to H2O2 Production

Abstract Achieving high selectivity of glyceraldehyde (GLD) products remained challenging due to competing C─C bond cleavage and multiple reaction pathways during glycerol electrooxidation. Herein, we designed a PtSb single‐atom alloy supported on non‐stoichiometric TiO 2 (PtSb 1 /TiO x ), which enabled highly efficient and stable GLD production under neutral conditions. The catalyst achieved 87% GLD selectivity with exceptional stability exceeding 120 h. TiO x support suppressed C─C bond cleavage, preserving C 3 intermediates, while atomic Sb dispersed in the Pt matrix enhanced GLD selectivity. This further stabilized active sites through Pt─Sb bond formation, which mitigated oxidative deactivation. We integrated PtSb 1 /TiO x with a Pt‐loaded ZnFeWMn medium‐entropy oxide for two‐electron oxygen reduction, enabling simultaneous production of C 3 and H 2 O 2 products. In a membrane‐electrode assembly system under neutral conditions, this achieved yields of 0.332 mmol h −1 for GLD and 0.50 mmol h −1 for H 2 O 2 . In alkaline media, by controlling H 2 O 2 transport, the system attained 72.9% glycerate selectivity without external bias, representing one of the most efficient bias‐free glycerol valorization systems reported. This work pioneered a dual‐strategy approach for catalyst engineering to control reaction pathways and system integration for simultaneous high‐value chemical production.