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<p>Porphyrin-based materials are attractive due to their adaptable photochemical and photophysical properties, it is also attainable through strategic organic group modifications. Therefore, the incorporation of porphyrins into inorganic materials yields distinct adsorption, catalytic, and sensing capabilities. This research focuses on modifying ZrO<sub>2</sub> and TiO<sub>2</sub> xerogels using organoalkoxysilanes bearing alkyl and aryl groups, and 5, 10, 15, 20-<i>meso-tetrakis</i>-<i>(para-carboxy</i>phenyl) porphyrin, H<sub>2</sub>T(<i>p-</i>COOH)PP, as the active molecule. Near-infrared spectroscopy (NIR) confirmed the attachment of alkyl and aryl groups to the porphyrin <i>via</i> weak interactions. Nitrogen gas adsorption was carried out to characterize pore size and surface areas, while UV-vis and fluorescence spectroscopy monitored changes during the transition from jellifying mixtures to solids, the optimization of fluorescence and textural properties in organo-modified ZrO<sub>2</sub> and TiO<sub>2</sub> xerogels revealed notable trends such as restricted pore accessibility, and a corresponding decrease in specific surface area particularly with large organic groups. In the case of TiO<sub>2</sub> samples modified with alkyl or aryl groups they exhibited increased pore widths, ZrO<sub>2</sub> networks featuring dodecyl groups displayed larger pores. These findings emphasize the significant impact of the oxide network and the presence of large organic groups on the emission process. A comparative analysis with analogous SiO<sub>2</sub> systems provides further insight into material properties and future applications in luminescence, sensors and medical devices.</p>

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Design and synthesis of porphyrin-based hybrid materials via organofunctionalization of ZrO2 and TiO2

  • 期刊论文

  • 发表日期：

    2025年7月26日

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  • Eduardo Salas-Bañales,
  • R. Iris Y. Quiroz-Segoviano,
  • Alberto Estrella-González,
  • Jonathan Osiris Vicente-Escobar,
  • Berenice González-Santiago,
  • Miguel Ángel García-Sánchez

摘要

Porphyrin-based materials are attractive due to their adaptable photochemical and photophysical properties, it is also attainable through strategic organic group modifications. Therefore, the incorporation of porphyrins into inorganic materials yields distinct adsorption, catalytic, and sensing capabilities. This research focuses on modifying ZrO2 and TiO2 xerogels using organoalkoxysilanes bearing alkyl and aryl groups, and 5, 10, 15, 20-meso-tetrakis-(para-carboxyphenyl) porphyrin, H2T(p-COOH)PP, as the active molecule. Near-infrared spectroscopy (NIR) confirmed the attachment of alkyl and aryl groups to the porphyrin via weak interactions. Nitrogen gas adsorption was carried out to characterize pore size and surface areas, while UV-vis and fluorescence spectroscopy monitored changes during the transition from jellifying mixtures to solids, the optimization of fluorescence and textural properties in organo-modified ZrO2 and TiO2 xerogels revealed notable trends such as restricted pore accessibility, and a corresponding decrease in specific surface area particularly with large organic groups. In the case of TiO2 samples modified with alkyl or aryl groups they exhibited increased pore widths, ZrO2 networks featuring dodecyl groups displayed larger pores. These findings emphasize the significant impact of the oxide network and the presence of large organic groups on the emission process. A comparative analysis with analogous SiO2 systems provides further insight into material properties and future applications in luminescence, sensors and medical devices.