The In Situ Electrochemical−Chemical Cascade Strategy for Pyruvic Acid Synthesis

Abstract

ABSTRACT Hydrogen peroxide (H2O2), as a green oxidizing medium, can be generated and utilized in situ via an electrochemical–chemical cascade, enabling organic transformations while enhancing efficiency and selectivity. However, balancing high H2O2 production, efficient activation, and selective substrate conversion remains challenging. Herein, a series of transition metal‐doped CeO2 catalysts were developed for electrocatalytic H2O2 generation and its subsequent use in converting α‐hydroxy acids to pyruvate. Among them, Ni−CeO2 exhibited the best performance, achieving a pyruvate production rate of 19.9 mmol g−1 h−1 and a Faradaic efficiency of 55.3%. Mechanistic studies revealed that transition metal doping regulates the local coordination environment and oxygen vacancy concentration, thereby optimizing the adsorption strength of the *OOH intermediate, which governs the two‐electron oxygen reduction reaction pathway and H2O2 generation and release. Furthermore, in situ generated H2O2 was selectively activated on the catalyst surface to form a reactive oxygen species network dominated by hydroxyl radicals (·OH) and assisted by singlet oxygen (1O2). Among these, ·OH showed the lowest energy barrier for α‐C─H bond activation and subsequent electron rearrangement, making it the key species for pyruvate formation. This work provides a new strategy for the preparation of value−added chemicals.