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Zn2+ doped ormosil–phosphotungstate hybrid films with enhanced photochromic response

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Abstract

Owing to the wide use of photochromic materials in UV sensors and dosimeters, considerable efforts have been made to increase the UV-response and sensitivity of the existing classes of photochromic materials. In this study, we report a simple sol–gel route for the preparation of highly photochromic transparent films based on ormosil–phosphotungstate hybrid materials. The effect of addition of Zn2+ ions on the photochromic response of these hybrid films and the possible mechanism involved is discussed. Compared to the undoped samples, the photochromic response of the Zn2+-doped hybrid films increases by 59–237 % depending on the concentration of Zn2+ ions added to the sol formulation. No structural or electronic change in the phosphotungstate dye was observed by vibrational spectroscopy or UV spectroscopy, though micro X-ray fluorescence (μ-XRF) analysis showed that the addition of Zn2+ in the sol–gel preparations leads to an increase in the amount of phosphotungstate (HPW) incorporated in the dip-coated films. Furthermore, TEM and nano-energy-dispersive X-ray showed formation of nano-agglomerates consisting of Zn and HPW in the Zn2+-doped samples. Zn K-edge X-ray absorption near edge structure analysis also confirmed the formation of the salt Hx[Zn(OH2)6] 2−xPW12O40. It is suggested that these Zn-phosphotungstate nano-agglomerates get trapped into the ormosil network during films preparation leading to increased concentration of the phosphotungstate anions in the films, in accordance with results from μ-XRF analysis. Raman spectroscopy confirmed that the Keggin structure of HPW is preserved in the hybrid films. FTIR spectra of the matrix part of the samples are identical before and after UV-irradiation, which suggests that the photochromic process does not involve oxidation of the organic functionalities. These highly photochromic hybrid films are promising candidates for the design of practical UV-sensing devices and dosimeters.

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Acknowledgments

The authors thank The São Paulo Research Foundation, FAPESP, research grant 2011/08120-0, CNPq and CAPES. Sajjad Ullah thanks the Third World Academy of Science (TWAS, Italy) and the National Council for Scientific and Technological Development (CNPq, Brazil) for Ph. D. fellowship. We also thank the Brazilian National Synchroton Light Laboratory (LNLS-Campinas Brazil) for providing the facility of micro X-ray fluorescence and XANES analysis. The XANES measurements were performed under the Project # XAFS1-15185. The μ-XRF measurements were performed under the Project XAFS1-14257.

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  1. Instituto de Química de São Carlos, Universidade de São Paulo, São Carlos, 13560-970, Brazil

    Elias Paiva Ferreira-Neto, Sajjad Ullah, Orlando Armando Elguera Ysnaga & Ubirajara Pereira Rodrigues-Filho

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  1. Elias Paiva Ferreira-Neto
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  2. Sajjad Ullah
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  3. Orlando Armando Elguera Ysnaga
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  4. Ubirajara Pereira Rodrigues-Filho
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Correspondence to Ubirajara Pereira Rodrigues-Filho.

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Ferreira-Neto, E.P., Ullah, S., Ysnaga, O.A.E. et al. Zn2+ doped ormosil–phosphotungstate hybrid films with enhanced photochromic response. J Sol-Gel Sci Technol 72, 290–300 (2014). https://doi.org/10.1007/s10971-014-3404-7

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