Advances in Electrocatalytic Valorization of Glycerol: From Fundamental Understanding to Practical Innovation

ABSTRACT Glycerol, a major byproduct of biodiesel production, is generated in significant excess, leading to a sharp decrease in its market value and underscoring the urgent need for efficient valorization strategies. The glycerol electrooxidation reaction (GEOR) has emerged as a promising electrocatalytic pathway for converting low‐cost glycerol into high‐value chemicals, offering a sustainable route for biomass upgrading while advancing energy‐efficient electrochemical conversion and green synthesis. This review provides a comprehensive summary of recent advances in GEOR research, focusing on the rational design of high‐performance electrocatalysts, optimization of electrolytic environments, and mechanistic elucidation of reaction pathways. These insights collectively aim to inform the development of GEOR systems with high current density, selectivity, Faradaic efficiency, and operational stability. The synergistic integration of GEOR with complementary reactions—including hydrogen evolution, CO 2 reduction, and nitrate reduction is also examined. Furthermore, the potential of flow electrolyzers to mitigate mass‐transport limitations and enhance overall reaction efficiency is highlighted. A techno‐economic analysis is presented to assess the industrial feasibility and economic competitiveness of emerging GEOR technologies. Finally, this review identifies key challenges and outlines future research directions intended to accelerate the transition of GEOR from fundamental studies to practical, scalable applications.