Boosting H(2)O(2) synthesis for fenton oxidation process via the synergy of Z-scheme porphyrin-Zn/Cu MOF@ZnSiO(3) piezo-photocatalytic system.

Metal-organic frameworks (MOFs) serve as one of the most promising candidates for H₂O₂ photosynthesis from water, but suffer insufficient separation of photogenerated charges and slow carrier transfer. Herein, we construct a piezoelectric heterojunction involving supramolecular bi-metallic copper/zinc tetrakis (4-carboxyphenyl) porphyrin and zinc silicate (abbr. ZnSi/Cu(Zn)-TCPP), which enhances charge kinetics related to photogenerated charge separation and transfer. Theoretical/experimental results reveal that the atomically dispersed CuZn units in the Cu(Zn)-TCPP amplify piezoelectric response under ultrasonication, and the tandem interfacial electric field facilitates a Z-scheme electron transfer. Without sacrificial agents, ZnSi/Cu(Zn)-TCPP exhibits a high apparent quantum efficiency of 45.09 % at 420 nm under concurrent ultrasonic and light irradiation. Computational simulations further reveal that the interfacial coupling effects of ZnSi/Cu(Zn)-TCPP optimize oxygen adsorption energy and lower water oxidation (WOR) barriers, thus facilitating the separated redox reactions of 2e oxygen reduction (ORR) and 2e WOR. Furthermore, the in-situ generated HO by ZnSi/Cu(Zn)-TCPP (0.025 g) activates a self-Fenton process with Fe(II) (0.4 mmol/L), enabling high-efficiency degradation and mineralization of antibiotics, such as ciprofloxacin (CIP, 95.6 % degradation (50 mL, 50 mg/L) and 92.3 % TOC removal). This work demonstrates atomic-level bimetallic polarization engineering in MOFs, offering new insights for multi-field coupled catalysis in green synthesis and environmental remediation.