Electrocatalytic glycerol valorization: From catalyst design to integrated systems

The electrochemical oxidation of glycerol (GOR) has emerged as a sustainable pathway for transforming biodiesel byproducts into valuable resources, while addressing the growing demand for renewable energy and green chemical production. This perspective provides a comprehensive examination of recent advances in GOR technology, with a particular emphasis on catalyst design, reaction mechanisms, and system integration strategies. It highlights key challenges related to selectivity, stability, and scalability, which are critical for advancing the technology toward industrial applications. We explore how both noble metals (<em>e.g.</em>, Pt, Au, Pd) and non-noble metal alternatives (<em>e.g</em>., Ni, Co, Cu) can be engineered through various methods, such as facet control, single-atom incorporation, and dynamic potential modulation, to selectively preserve C-C bonds and direct selectivity toward valuable multi-carbon products. Beyond standalone GOR processes, the integration with cathodic reactions presents new opportunities for system-level optimization. We discuss the benefits of coupling GOR with cathodic reactions, such as hydrogen evolution (HER), carbon dioxide reduction (CO₂RR), and nitrate reduction (NO₃RR), which not only reduce energy consumption but also enable the co-production of high-value chemicals and clean fuels. Despite the significant progress in GOR technology, several critical challenges remain for its industrial implementation, including mass transfer limitations, tolerance to crude glycerol, and long-term stability. This perspective provides a roadmap for addressing these challenges, proposing targeted solutions ranging from advanced membrane-electrode assemblies to integrated techno-economic assessments. Ultimately, this work aims to guide the field beyond a focus on catalyst activity, toward a holistic paradigm that prioritizes system-level integration and economic viability, thereby accelerating the industrialization of GOR technology.