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Photocatalytic activity enhancement of two-step and one-pot synthesis of Pd/ZnO nanocomposites: an experimental and DFT study

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Abstract

Pd/ZnO nanocomposites were successfully synthesized by means of one and two pot synthesis and applied in the photodegradation of Rh6G. The nanocomposites were characterized by XRD, SEM, TEM, FTIR and micro-Raman spectroscopies. It was found the presence of PdZn2, PdO and agglomerated particles in the support surface for the Palladium-based nanocomposites fabricated by one-pot route; the two-step method allowed the formation of spherical Pd nanoparticles, with homogeneous distribution in the nanocomposite matrix, with an average size of 2.16 nm. The results show higher photocatalytic efficiency for the samples fabricated under the two-step approach compared to the one-pot synthesis. Based on experimental results, density functional theory (DFT) calculations were carried out to understand the enhancement photocatalytic of Pd/ZnO nanocomposites. To achieve it, the ZnO (001) and (101) surfaces were built and decorated by different Pd coverages. The theoretical results indicated two different photocatalytic mechanisms. In ZnO (001) case, the electrons flowed from surface to Pd, generating the superoxide radical anion (⋅O2−). Furthermore, the density of states of the ZnO (001) surface was modified by impurity Pd–d states at proximity to the conduction states, which may work as electron acceptors states. On the other hand, we found that the electrons flow from Pd to ZnO (101) surface, inducing the formation of ⋅OH and ⋅O2− for the degradation of Rh6G. The density of states of the ZnO (101) revealed a reduction in its bandgap, due to Pd–d states localized above valence states. Hence, our theoretical results suggest that the Pd–d states may facilitate the mobility of electrons and holes in (001) and (101) surfaces, respectively, reducing the rate of charge recombination.

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Acknowledgements

The authors gratefully acknowledge to Laboratorio central IFUAP, for materials characterization, and the computer resources provided by Laboratorio Nacional de Supercómputo del Sureste de México (LNS) (Project 202302046C), a member of the CONAHCYT network of Nacional Laboratories. J.C.M thanks to CONAHCYT for the doctoral scholarship.

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  1. Facultad de Ingeniería Química, Benemérita Universidad Autónoma de Puebla, C.P. 72570, Puebla, Pue., Mexico

    María de Lourdes Ruiz Peralta, C. E. Rocha-Díaz, J. H. Camacho-García & A. Escobedo-Morales

  2. Instituto de Física, Benemérita Universidad Autónoma de Puebla, Apdo. Postal J-48, 72570, Puebla, Pue., Mexico

    J. C. Moreno-Hernandez & U. Salazar-Kuri

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  1. María de Lourdes Ruiz Peralta
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de Lourdes Ruiz Peralta, M., Moreno-Hernandez, J.C., Rocha-Díaz, C.E. et al. Photocatalytic activity enhancement of two-step and one-pot synthesis of Pd/ZnO nanocomposites: an experimental and DFT study. Photochem Photobiol Sci (2024). https://doi.org/10.1007/s43630-024-00562-1

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