C.Y. Li, T. Azam, S.W. Li, Y.H. Fu, M.T. Zhang, X. Wang, Y.J. Zhou and Z.-S. Wu *

ChemSusChem, 2025, accepted.

As a major by-product of biodiesel production, glycerol offers significant economic potential when effectively utilized. The electrooxidation of glycerol to formic acid in couped systems has attracted considerable attentions due to its environmental friendliness, cost-effectiveness, low energy consumption and production of high-value-added chemicals. This concept presents the key strategies for catalyst design and rational construction of representative coupled systems towards the efficient electrooxidation of glycerol to formic acid. Firstly, we overview the key catalyst design strategies from four aspects, including heteroatom doping, vacancy engineering, interface engineering, and component engineering, to construct highly active sites and tune the electronic properties of electrocatalysts. Subsequently, we discuss the representative coupled systems for glycerol oxidation to formic acid, highlight the importance of electrooxidation to high-value added chemicals. Finally, we conclude by outlining current challenges and proposing future perspectives, to arouse further research interest and facilitate further development.