Efficient Dual‐Path Piezosynthesis of Hydrogen Peroxide by Breaking Symmetry of UiO‐66

ABSTRACT Piezocatalysis of non‐centrosymmetric crystals presents a promising strategy for the sustainable synthesis of hydrogen peroxide (H 2 O 2 ). However, the efficiency of H 2 O 2 piezosynthesis remains constrained by the high activation barrier for water (H 2 O) decomposition and weak oxygen (O 2 ) adsorption. Herein, we rationally designed the bimetallic UiO‐66(Hf x Zr 6‐x ) piezocatalysts through symmetry breaking of the metal clusters, thereby inducing piezoelectricity into this intrinsically centrosymmetric metal–organic framework (MOF). We demonstrate that the symmetry breaking induced active sites in UiO‐66(Hf 3 Zr 3 ) can strengthen H 2 O/O 2 binding affinity and facilitate radical generation, while the piezoelectric field substantially reduces the reaction energy barrier for H 2 O 2 formation. Especially, the optimized UiO‐66(Hf 3 Zr 3 ) piezocatalysts exhibit a suitable band structure and abundant defects, significantly enhancing piezoelectric polarization induced charge carrier separation and thereby boosting the dual‐pathway generation of H 2 O 2 . This MOF‐based piezocatalyst achieves a sacrificial reagent‐free H 2 O 2 production rate of 4.8 mmol g − 1 h − 1 directly from air and water, while maintaining continuous operation for 15 h. This work establishes a generalized strategy for inducing piezoelectricity in centrosymmetric MOFs and advancing their sustainable catalytic applications, paving the way for the design of MOF‐based piezoelectric materials with efficient charge separation and high catalytic performance.