This thesis investigates the electrooxidation of glycerol (GEOR) as a sustainable alternative to the oxygen evolution reaction for hydrogen production and biomass valorization. The work integrates three complementary approaches: (i) studying the effect of applied current density on product selectivity and reaction kinetics using nickel electrodes, (ii) exploring silicon-based photoelectrodes modified with Ni, Au, and PdAu to enhance light-driven glycerol oxidation and enable bias-free operation in flow photoelectrochemical reactors, and (iii) developing and validating an HPLC analytical method for accurate identification and quantification of key oxidation products. Spectroelectrochemical and kinetic analyses reveal the interplay between surface oxidation states, charge transfer, and product distribution. Overall, this research provides mechanistic insight and methodological advances that contribute to the rational design of efficient (photo)electrochemical systems for concurrent hydrogen generation and production of high-value chemicals from glycerol.
