关键词: 压电催化, 掺杂, 过一硫酸盐, 卡马西平, 污染物降解

The piezoelectric-coupled peroxymonosulfate (PMS) advanced oxidation process, which harnesses mechanical energy to generate reactive oxygen species, holds great promise for the remediation of emerging pharmaceutical pollutants. In this work, Co-doped ZnO piezocatalysts with varying Co doping levels were fabricated via a one-step hydrothermal method, and their catalytic performance for PMS activation was systematically investigated using carbamazepine (CBZ) as the target pollutant. X-ray diffraction and Raman spectroscopy confirmed the successful substitutional doping of Co²⁺ into the ZnO lattice, inducing lattice distortion and enhancing non-centrosymmetry. Piezoresponse force microscopy revealed a typical piezoelectric response for 2-Co/ZnO with a d₃₃ coefficient of approximately 58 pm•V^–1. Electrochemical measurements demonstrated that Co doping significantly increased the piezoelectric current density and reduced the charge transfer resistance. Under optimized conditions (catalyst dosage: 0.6 g•L^–1, PMS concentration: 0.1 g•L^–1, ultrasonic power: 240 W), the 2-Co/ZnO/PMS/US system achieved 94% degradation of 10 mg•L^–1 CBZ within 60 min, with a pseudo-first-order rate constant of 0.04 min^–1. Radical quenching experiments and electron paramagnetic resonance spectroscopy identified singlet oxygen (¹O₂) as the dominant reactive species, with a non-radical pathway contributing over 60% to the overall degradation. The system exhibited robust catalytic activity across a wide pH range (3-9) and in the presence of various coexisting ions. Recycling tests showed that the catalyst retained 81.2% of its initial activity after four consecutive cycles. Based on liquid chromatography-mass spectrometry (LC-MS) intermediate identification and density functional theory (DFT) Fukui function calculations, two oxidative mineralization pathways for CBZ were proposed, involving hydroxylation, oxidation, and ring-opening reactions, with the C(11) and C(12) sites (f⁰=0.0746 and 0.0755, respectively) identified as the most vulnerable reactive centers. Finally, the 2-Co/ZnO powder was incorporated into a PVDF composite catalytic membrane via electrospinning, which achieved 89% CBZ removal under simulated low-frequency natural water flow conditions, demonstrating favorable cycling stability and economic feasibility. This study provides both theoretical insights and experimental support for the engineering application of piezocatalysis-coupled PMS activation technology in the remediation of recalcitrant organic pollutants in natural water bodies.

Key words: piezocatalysis, doping, peroxymonosulfate, carbamazepine, pollutant degradation