Synergistic catalytic activation of persulfate by CuMnO(2)-CoPc heterostructures on Ti foam: kinetics and mechanism of antibiotic oxidation

CuMnO(2)-CoPc异质结构在钛泡沫上对过硫酸盐的协同催化活化:抗生素氧化的动力学和机理

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Abstract

This study presents a novel heterogeneous catalyst system - CuMnO(2)@cobalt phthalocyanine immobilized on titanium foam (CuMnO(2)@CoPc/Ti foam) - that is highly effective in treating three common antibiotics, ofloxacin (OFL), levofloxacin (LEVO) and sulfanilamide (SFA), through UV-persulfate-based advanced oxidation (UV/PS). Comprehensive characterization (XRD, SEM-EDS, FTIR, BET, XPS, and UV-vis DRS) confirms a stable mesoporous architecture and uniform coating; the specific surface area increases from 55.3 to 60.8 m(2) g(-1) after CoPc deposition, and the apparent optical band gap narrows from ≈1.41 to ≈1.31 eV, indicating improved visible-light response. Antibiotic decay follows pseudo-first-order kinetics with k (app) of 0.0426 ± 0.0015, 0.0410 ± 0.0017, and 0.0393 ± 0.0013 min(-1) for OFL, LEVO, and SFA, respectively, delivering >90% removal in 60 min. TOC mineralization reaches ≈69-72%, evidencing deep oxidation beyond parent-compound loss. Mechanistically, XPS verifies persistent Cu(2+)/Cu(+) and Mn(4+)/Mn(3+) surface couples (Co states stable), while EPR with DMPO detects SO(4)˙(-) and ˙OH, with sulfate radicals dominating. The monolithic catalyst is reusable over 5 cycles with negligible activity loss and ultra-low metal leaching (Cu/Mn/Co ≪ 0.1 mg L(-1) by ICP-OES), underscoring chemical robustness. These results highlight CuMnO(2)@CoPc/Ti foam as a durable, separable platform for UV/PS treatment of antibiotic-bearing waters and provide a mechanistic blueprint-combining photosensitization and multi-center redox-to guide future reactor-scale implementations.

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