Adsorbed Oxygen‐Induced d‐p Orbital Hybridization for Piezocatalytic H ₂ O ₂ Production, Antibiotic Degradation and Detoxification

ABSTRACT

Developing efficient water purification technologies without external chemical inputs is critical for treating emerging contaminants. Herein, we report a Cu ₂ WS ₄ ‐CoPc composite piezocatalyst that enables efficient in situ H ₂ O ₂ production and pollutant degradation via enhanced oxygen activation. The introduction of CoPc induces interfacial electron transfer from Cu ₂ WS ₄ to CoPc and promotes O ₂ activation through d‐p orbital hybridization between Co and O ₂ , as confirmed by density functional theory calculations showing a decrease in O ₂ adsorption energy from +1.2 to −0.3 eV. Consequently, the composite exhibits significantly enhanced piezoelectric response, with increased piezoelectric constant and effective longitudinal piezoelectric coefficient. The optimized Cu ₂ WS ₄ ‐CoPc generates H ₂ O ₂ via a two‐electron oxygen reduction pathway, with superoxide radicals (·O ₂ ⁻ ) as the key intermediate, achieving a yield of 183.4 µM within 30 min, which far exceeds that of pristine Cu ₂ WS ₄ . Moreover, the catalyst degrades ciprofloxacin with a rate constant of 0.059 min ⁻¹ , approximately 4.5 times higher than pure Cu ₂ WS ₄ , and zebrafish toxicity assays confirm effective detoxification of degradation intermediates. This study provides a new strategy for enhancing piezocatalytic H ₂ O ₂ synthesis through strengthened oxygen activation and lays a theoretical foundation for designing efficient, environmentally benign water treatment technologies.