Environmentally friendly loading of palladium nanoparticles on nanoporous PET track-etched membranes grafted by poly(1-vinyl-2-pyrrolidone) via RAFT polymerization for the photocatalytic degradation of metronidazole

Abstract

Nanoporous track-etched membranes (TeMs) are highly versatile materials that have shown promise in various applications such as filtration, separation, adsorption, and catalysis due to their mechanical integrity and high surface area. The performance of TeMs as catalysts for removing toxic pollutants is greatly influenced by the pore diameter, density, and functionalization of the nanochannels. In this study, the synthesis of functionalized poly(ethylene terephthalate) (PET) TeMs with Pd nanoparticles (NPs) as catalysts for the photodegradation of the antibiotic metronidazole (MTZ) was methodically investigated and their catalytic activity under UV irradiation was compared. Before loading of the Pd NPs, the surface and nanopore walls of the PET TeMs were grafted by poly(1-vinyl-2-pyrrolidone) (PVP) via UV-initiated reversible addition fragmentation chain transfer (RAFT)-mediated graft copolymerization. The use of RAFT polymerization allowed for precise control over the degree of grafting and graft lengths within the nanochannels of PVP grafted PET TeMs (PVP-g-PET). Pd NPs were then loaded onto PVP-g-PET using several environmentally friendly reducing agents such as ascorbic acid, sodium borohydride and a plant extract. In addition, a conventional thermal reduction technique was also applied for the reduction of the Pd NPs. The grafting process created a surface with high-sorption capacity for MTZ and also high stabilizing effect for Pd NPs due to the functional PVP chains on the PET substrate. The structure and composition of the composite membranes were elucidated by scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, thermogravimetry, contact angle measurements and energy dispersive X-ray (EDX), X-ray photoelectron (XPS) and Fourier transform infra-red (FTIR) spectroscopies. The effects of different types of reducing agents, pH, the amount of loaded catalyst and MTZ concentration on the MTZ catalytic degradation efficiency of the obtained composites were investigated. The efficiency of the catalyst prepared in the presence of ascorbic acid was superior to the others (89.86% removal at 30 mg L⁻¹ of MTZ). Maximum removal of MTZ was observed at the natural pH (6.5) of the MTZ solution at a concentration of 30 mg per L MTZ. The removal efficiency was decreased by increasing the catalyst dosage and the initial MTZ concentration. The reaction rate constant was reduced from 0.0144 to 0.0096 min⁻¹ by increasing the MTZ concentration from 20 to 50 mg L⁻¹. The photocatalyst revealed remarkable photocatalytic activity even after 10 consecutive cycles.