Abstract
In this work, we propose zinc oxide (ZnO) surface functionalization with plasmonic silver nanoparticles (AgNP) of different sizes and shapes (spheres, prisms, and rods) creating ZnO/AgNP nanohybrids. These were characterized by UV-Vis spectroscopy, X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectroscopy, diffuse reflectance spectroscopy, and photoluminescence spectroscopy. Surface functionalization with AgNP improved photocatalyst electronic properties, its visible light absorption, and slow electron/hole recombination on the ZnO surface. Photocatalysis assays performed with a polychromatic Hg lamp degraded methyl orange, a model of persistent organic pollutant in water. A systematic study showed that the photodegradation kinetics of the nanohybrids are significantly more efficient than pure ZnO (up to 18 times) and that AgNP size and especially its shape are important in dye degradation. Mechanistic studies revealed that degradation occurred by direct dye reduction on the ZnO surface holes, ZnO electron transfer to Ag followed by •O2− formation, and direct injection of AgNP hot electrons in the ZnO conduction band. The last effect was stronger for anisotropic AgNP, which explains their high kinetic degradation rates. Therefore, the rational design in ZnO/AgNP nanohybrid engineering and a systematic approach used in this manuscript allowed a detailed description of photodegradation process that occur at ZnO/AgNP interface. Our results are not conclusive about AgNP size; on the other hand, it clearly demonstrates that anisotropic nanoparticles (as Ag rods and prims) present superior photodegradation efficiency and are promising particles for further large-scale use of solar-irradiated nanohybrids.
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Acknowledgements
This research used facilities of the Brazilian Nanotechnology National Laboratory (LNNano), part of the Brazilian Centre for Research in Energy and Materials (CNPEM), a private non-profit organization under the supervision of the Brazilian Ministry for Science, Technology, and Innovations (MCTI). The TEM-MSC staff is acknowledged for the assistance during the experiments (proposal ID #20210218). The authors also would like to thank Dr. Douglas Santana Franciscato for DLS measurements.
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This work was supported by the Brazilian agency Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) (process number 2019/01604-3 and 2020/03388-3).
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All authors contributed to the study conception and design. Material preparation, data collection, and analysis were performed by Danielle Ramos Mota and William da Silva Martini. The first draft of the manuscript was written by Danielle Ramos Mota and William da Silva Martini and fully revised by Diogo Silva Pellosi. All authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
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Mota, D.R., Martini, W.d. & Pellosi, D.S. Influence of Ag size and shape in dye photodegradation using silver nanoparticle/ZnO nanohybrids and polychromatic light. Environ Sci Pollut Res 30, 57667–57682 (2023). https://doi.org/10.1007/s11356-023-26580-7
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DOI: https://doi.org/10.1007/s11356-023-26580-7