Piezocatalytic Generation of Hydrogen Peroxide Over UiO‐66: Effect of Metal Centers Modulation

ABSTRACT Hydrogen peroxide (H₂O₂) exhibits significant market demand given its versatile applications. However, the conventional anthraquinone‐based production process suffers from high energy consumption and the generation of toxic by‐products. Piezocatalysis, capable of converting external mechanical energy into chemical energy, offers a highly promising method for producing H₂O₂. In this study, we thoroughly explored the intrinsic effect of metal centers in a typical metal–organic framework UiO‐66. X‐UiO‐66 (X = Hf, Zr, Ce) was successfully synthesized and assessed for piezocatalytic H₂O₂ production. Among the three samples, Hf‐UiO‐66 exhibited the best piezoresponse to ultrasonic radiation with an extraordinary piezoelectric coefficient of 1.1 nm V −1 , achieving an H₂O₂ hourly yield of 827.6 μmol g −1 under ultrasonic vibration and vigorous stirring. Mechanism study revealed that the piezocatalytic H₂O₂ formation was primarily an oxygen reduction process that occurred via a two‐electron transfer pathway, during which the piezoresponse significantly enhanced the carrier separation and transportation. Additionally, the piezoelectric effect played a crucial role in facilitating charge carrier separation during the reaction. This work contributes to the rational design and continuous improvement of MOF catalysts, enhancing their applicability for diverse catalytic applications.