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<p>Photocatalytic activity of rutile was intentionally reduced by band gap engineering with the aim of developing the safe and stable UV filter formulations. The samples of rutile were doped with 2.5&#xa0;mol% of Ce<sup>3+</sup>, Mn<sup>2+</sup>, Al<sup>3+</sup>, and Mg<sup>2+</sup> via chemical co-precipitation at pH = 10–11 with subsequent heat treatment at 350&#xa0;°C. Photocatalytic degradation of phenol demonstrated pronounced inhibition: Mg<sup>2+</sup> completely suppressed activity, Mn<sup>2+</sup> reduced it fourfold, and Ce<sup>3+</sup> and Al<sup>3+</sup> caused moderate decreases. X-ray diffraction revealed dopant-induced changes in lattice parameters. Diffuse reflectance spectroscopy (Kubelka–Munk analysis) showed a band gap narrowing (0.05–0.10&#xa0;eV) and a conduction band edge shift (+ 0.01–0.06&#xa0;V(SHE)). Positive conduction band edge shift vs. О<sub>2</sub>/О<sub>2</sub>· process causes minimal ROS generation for Mn<sup>2+</sup> and Mg<sup>2+</sup>-doped rutile samples. The screening surface states’ effect has the most distinct inhibition contribution for Mg(OH)<sub>2</sub>-to-MgO transition at around 350&#xa0;°C. This counter-intuitive inhibition, contrasting with most doping studies aiming at enhancement of activity, supports Mg- and Mn-modified rutile as promising candidates for physical UV filters.</p>

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Inhibition of photocatalytic phenol degradation by doped rutile TiO2: toward more safe and stable UV filter formulations

  • 期刊论文

  • 发表日期：

    2026年2月14日

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  • Olga Hlushko,
  • Georgii Sokolsky,
  • Oleksandr Shtyka,
  • Waldemar Maniukiewicz,
  • Tomasz Maniecki

摘要

Photocatalytic activity of rutile was intentionally reduced by band gap engineering with the aim of developing the safe and stable UV filter formulations. The samples of rutile were doped with 2.5 mol% of Ce3+, Mn2+, Al3+, and Mg2+ via chemical co-precipitation at pH = 10–11 with subsequent heat treatment at 350 °C. Photocatalytic degradation of phenol demonstrated pronounced inhibition: Mg2+ completely suppressed activity, Mn2+ reduced it fourfold, and Ce3+ and Al3+ caused moderate decreases. X-ray diffraction revealed dopant-induced changes in lattice parameters. Diffuse reflectance spectroscopy (Kubelka–Munk analysis) showed a band gap narrowing (0.05–0.10 eV) and a conduction band edge shift (+ 0.01–0.06 V(SHE)). Positive conduction band edge shift vs. О2/О2· process causes minimal ROS generation for Mn2+ and Mg2+-doped rutile samples. The screening surface states’ effect has the most distinct inhibition contribution for Mg(OH)2-to-MgO transition at around 350 °C. This counter-intuitive inhibition, contrasting with most doping studies aiming at enhancement of activity, supports Mg- and Mn-modified rutile as promising candidates for physical UV filters.