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Experimental and Theoretical Correlation of Modulated Architectures of β-Ag2MoO4 Microcrystals: Effect of Different Synthesis Routes on the Morphology, Optical, Colorimetric, and Photocatalytic Properties

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Abstract

In this paper, the effect of different synthesis methods, such as controlled precipitation (CP), sonochemical, hot solution ion injection with fast cooling, and conventional hydrothermal in obtaining beta-disilver molybdate (β-Ag2MoO4) are explained in details. X-ray diffraction patterns, Rietveld refinement data, cluster modeling, micro-Raman, and Fourier transform infrared spectroscopies confirmed that all β-Ag2MoO4 crystals have a spinel-like cubic structure, space group (Fd \(\overline{3 }\) m), and symmetry point group (\({O}_{h}^{7}\)). Field emission scanning electron microscopy (FE-SEM) images showed that through different synthetic routes, it is possible to obtain monophasic crystals, such as regular/irregular polyhedrons (cubes, cuboctahedron, trapezohedron, rhombic dodecahedron), potatoes, and non-uniform. The crystal shape observed experimentally was modeled based on Rietveld refinement data and FE-SEM images obtained by KrystalShaper program. First-principles quantum mechanical calculations based on density functional theory were employed to modulate the crystals’ surfaces and to obtain their surface energy (Esurf) values. From these Esurf values in association with the Wulff construction, the evolution of the crystals shape was achieved correlating with the experimental results when different synthesis methods are used. Ultraviolet–Visible (UV–Vis) spectroscopy measurements in absorbance mode showed three main absorptions (280, 310, and 340 nm), while the UV–Vis analyses in diffuse reflectance mode showed a tail of energy absorption in the UV spectrum range (3.25 eV and 3.3 eV). The quantitative data from the colorimetric analysis indicated that the β-Ag2MoO4 crystals are desirable for developing inorganic pigments with a beige to brown shade. Photocatalytic assays were performed using four lamps: UV-C, UV-B, UV-A, and visible light. The β-Ag2MoO4 crystals prepared by the CP method showed a higher degradation rate at 85.12% for the Rhodamine B dye solution under 240 min exposure to UV-C light.

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Data Availability

The data that support the findings of this study are available on request from the corresponding author.

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Acknowledgements

The authors thank CAPES, CNP, and FAPEPI for their financial support, UFG-CRTI for the FE-SEM analyses, UFPI-LIMAV, UFPI-FISMAT, GERATEC-UESPI, to CETEM and PET-Chemistry UESPI for technical support. A.F.G. acknowledges the Generalitat Valenciana (Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital) for the postdoctoral contract (CIAPOS/2021/106).

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Authors and Affiliations

  1. GERATEC-CETEM-PPGQ, Universidade Estadual do Piauí, Rua: João Cabral, N. 2231, P.O. Box 381, Teresina, PI, 64002-150, Brazil

    F. H. P. Lopes, A. C. S. Jucá & L. S. Cavalcante

  2. Programa de Pós-Graduação em Química–PPGQ, Universidade Federal do Piauí, Teresina, PI, 64049-550, Brazil

    L. F. G. Noleto & V. E. M. Vieira

  3. Programa de Pós-Graduação em Ciências e Engenharia dos Materiais-PPGCEM, Universidade Federal do Piauí, Teresina, PI, 64049-550, Brazil

    P. B. de Sousa, Y. L. Oliveira, K. R. B. S. Costa & L. S. Cavalcante

  4. Bacharelado Interdisciplinar em Ciência e Tecnologia (BICT), Universidade Federal do Maranhão, São Luís, MA, 65085-580, Brazil

    M. A. P. Almeida

  5. Department of Analytical and Physical Chemistry, University Jaume I, 12071, Castelló, Spain

    A. F. Gouveia

Authors
  1. F. H. P. Lopes
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  2. L. F. G. Noleto
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  3. V. E. M. Vieira
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  4. P. B. de Sousa
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  5. A. C. S. Jucá
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  6. Y. L. Oliveira
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  7. K. R. B. S. Costa
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  8. M. A. P. Almeida
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  9. A. F. Gouveia
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  10. L. S. Cavalcante
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Contributions

This manuscript was written through the contributions of all authors that agreed with this submission. FHPL, LFGN, PBdeS, VEMV, KRBSC, and ACSJ prepared the samples and performed the UV–Vis measurements and photocatalytic assays. FHPL and LSC performed the Rietveld refinement and structural analysis. KRBSC performed the Raman, and FT-IR measurements. YLO performed colorimetric measurements. MAPA, AFG, and LSC conceived the project. All authors participated in writing the manuscript and discussing all the results.

Corresponding author

Correspondence to L. S. Cavalcante.

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Lopes, F.H.P., Noleto, L.F.G., Vieira, V.E.M. et al. Experimental and Theoretical Correlation of Modulated Architectures of β-Ag2MoO4 Microcrystals: Effect of Different Synthesis Routes on the Morphology, Optical, Colorimetric, and Photocatalytic Properties. J Inorg Organomet Polym 33, 424–450 (2023). https://doi.org/10.1007/s10904-022-02509-4

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