Highly Efficient Electrocatalytic Oxidation of Biomass‐Based Furfuryl Alcohol Over Mesoporous Polydopamine

ABSTRACT Development of efficient strategies for biomass valorization is of great importance. Herein, mesoporous polydopamine (meso‐PDA) electrocatalyst was synthesized, and applied to the electrocatalytic oxidation of biomass‐based furfuryl alcohol (FA) to value‐added 6‐hydroxy‐2,3‐dihydro‐6H‐pyran‐3‐one (HDPO). The performance of meso‐PDA for FA oxidation in different electrolyte systems including organic, acidic, neutral, and alkaline aqueous systems was evaluated. The results demonstrated that meso‐PDA exhibited outstanding electrocatalytic performance in an organic electrolyte system toward the electrochemical oxidation of FA to HDPO, achieving a selectivity of 78.80%, a Faradaic efficiency of 67.58%, and an overall conversion of 96.44%. Mechanistic studies suggested that the organic system provides a less polarized interfacial environment and favors OH*‐involved FA oxidation, while also providing a mildly protic environment that avoids the pH‐dependent drawbacks observed in water systems, thus leading to superior performance. This work not only highlights the potential of mesoporous polydopamine in the high‐value electrocatalytic upgrading of FA but also provides important insights into the design of novel polymer‐based electrocatalytic systems.