Mechanistic Insights into Glycerol Electro-Oxidation in Alkaline Medium on M@Pt/C Catalysts Revealed by In Situ FTIR

The development of efficient catalysts for the glycerol oxidation reaction (GOR) is crucial for advancing direct glycerol fuel cells. This study provides mechanistic insights into the glycerol electro-oxidation reaction (GOR) on Co@Pt/C, Ni@Pt/C, and Sn@Pt/C catalysts using in situ FTIR spectroscopy. While the structural and electrochemical properties of these materials have been previously reported, their reaction pathways and product selectivity under alkaline conditions remain unclear. Electrochemical performance was evaluated through cyclic voltammetry (CV) and chronoamperometry (1.0 M KOH + 1.0 M glycerol), revealing that the bimetallic catalysts exhibited superior catalytic activity compared to Pt/C. Co@Pt/C demonstrated the highest performance, with a 7.5-fold increase in current density relative to Pt/C, followed by Sn@Pt/C (3.4-fold) and Ni@Pt/C (2.8-fold). In situ FTIR analysis identified key oxidation products, including C3, C2, and C1 species, with evidence of both partial and complete oxidation. These findings demonstrate that the core metal plays a key role in governing reaction pathways and C–C bond cleavage, providing important insights for the rational design of anode materials in direct glycerol fuel cells.