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

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 TiO₂ (PtSb₁/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 C₃ 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 PtSb₁/TiO_x with a Pt-loaded ZnFeWMn medium-entropy oxide for two-electron oxygen reduction, enabling simultaneous production of C₃ and H₂O₂ 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 H₂O₂. In alkaline media, by controlling H₂O₂ 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.