A tandem electro‐thermocatalysis platform for practical hydrogen peroxide‐mediated oxygenation reactions at high rates

Abstract Hydrogen peroxide (H 2 O 2 ) is a platform green oxidant for high‐value chemical synthesis, but its centralized production hinders its widespread use in a safe manner. Here, we describe a practical tandem electro‐thermochemical H 2 O 2 ‐mediated oxygenation platform for the synthesis of various high‐value oxygen‐containing compounds. The integration of solid‐electrolyte H 2 O 2 electrosynthesis with heterogeneous zeolite thermocatalysis enables atom‐efficient oxygenations without the need for downstream electrolytes or catalysts separation. A spatially decoupled tandem system integrating aqueous H 2 O 2 electrosynthesis with nonaqueous thermocatalysis offers independent optimization capabilities, thus maximizing the overall space–time yield (STY). With microfluidic packed‐bed intensification for heterogeneous thermocatalysis, this tandem system achieved H 2 O 2 ‐mediated oxygenation of thioesters to sulfoxide at a high current density (300 mA cm −2 ) and STY (7.07 mmol cm −3 h −1 ). Furthermore, the platform's broad applicability was showcased with titanium‐silicalite‐1 zeolite catalyzed olefin epoxidation and cyclohexanone oxime synthesis, underscoring its potential for diverse catalytic oxygenation applications.