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The effect of precipitation conditions on the morpho-structural and optical properties of some zinc oxidic based compounds

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Abstract

Despite the rapid development of a wide variety of materials, zinc oxidic based compounds remain important multifunctional materials. Optimization of synthesis parameters is an essential step in controlling the morpho-structural properties of nanomaterials. For example, preparation of high purity ZnO without additional calcination stage as well as achieving reproducible larger batches is still a great challenge of our days. In this study we report a simple synthesis route for ZnO nanoparticles at room temperature, without any additives and without additional calcination stages using diisopropylamine (DIA) as precipitating agent. The study is focused on changing the molar ratio, the volume and the flow rate of the reactants. Depending on the pH evolution, the phase composition can be controlled to form zinc oxide, zinc hydroxide or layered zinc acetate. Pure zinc oxide phase was obtained at pH ~8 with DIA excess at least of 3 mole. The changes of the morpho-structural and optical properties of samples were investigated by X-Ray diffraction, infrared spectroscopy, scanning electron microscopy, mineralogical optic microscopy, optical and photoluminescence spectroscopy. A better understanding of the crystalline phases formation was achieved using theoretical calculation (DFT) with a good match of the results with the experimental ones. Luminescent studies showed that the emission of ZnO is in green spectral domain at ~548 nm due to VO → VB transitions while the layered zinc acetate exhibits a much more complex blue emission at ~ 442 and 476 nm due to Zni contributions. The luminescent mechanism was proposed, in order to explain the luminescent behavior of samples.

Graphical Abstract

The pH evolution during the precipitation affects the morphology of the samples (layered, rounded aggregates). The blue or green luminescent emission is due to the presence of interstitial zinc (Zni) and oxygen vacancies (Vo) in layered zinc acetate or ZnO structures.

Highlights

  • ZnO, Zn(OH)2 and Zn5(OH)8(Ac)2∙4H2O were prepared by precipitation.

  • Preparative parameters were optimized for larger batches of ZnO.

  • The phase purity and structural parameters are affected by pH evolution.

  • Triangular, rounded, tetragonal bipyramid and lamellar structures were obtained.

  • Blue and green luminescence peaked at 442 and 550 nm is due to Zni and Vo defects.

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Authors contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by L.E. Muresan, I. Perhaita, A. M. V. Branzanic, C. Sarosi, L. Barbu-Tudoran, G. Borodi, I. Petean. The first draft of the manuscript was written by L.E. Muresan and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Funding

This work was supported by a grant of the Ministry of Research, Innovation and Digitization, CCCDI - UEFISCDI, project number PN-III-P2-2.1-PED-2021-2421, within PNCDI III and from the Romanian Ministry of Education and Research, PN-III-P1-1.1- PD-2021-0279 is gratefully acknowledged. The maintenance for the diffractometer was supported by the Ministry of Research, Innovation, and Digitization through Programme 1-Development of the National Research and Development System, Subprogramme 1.2-Institutional Performance-Funding Projects for Excellence in RDI, Contract No. 37PFE/30.12.2021.

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Authors and Affiliations

  1. “Raluca Ripan” Institute for Research in Chemistry, Babes-Bolyai University, Fântânele 30, 400294, Cluj-Napoca, Romania

    L. E. Mureşan, I. Perhaița, A. M. V. Brânzanic & C. Sarosi

  2. Electronic Microscopy Centre, Babes-Bolyai University, Clinicilor 5-7, 400006, Cluj-Napoca, Romania

    L. Barbu-Tudoran

  3. National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293, Cluj-Napoca, Romania

    L. Barbu-Tudoran & G. Borodi

  4. Faculty of Chemistry and Chemical Engineering, Babes-Bolyai University, 11 Arany Janos Street, 400028, Cluj-Napoca, Romania

    I. Petean

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Mureşan, L.E., Perhaița, I., Brânzanic, A.M.V. et al. The effect of precipitation conditions on the morpho-structural and optical properties of some zinc oxidic based compounds. J Sol-Gel Sci Technol 109, 795–809 (2024). https://doi.org/10.1007/s10971-024-06313-z

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