Impact of the absolute rutile fraction on TiO2 visible-light absorption and visible-light-promoted photocatalytic activity

• Autor(a) principal: Tobaldi, D.M.
• Data de Publicação: 2019
• Outros Autores: Lajaunie, L., Rozman, N., Caetano, A.P.F., Seabra, M.P., Sever Škapin, A., Arenal, R., Labrincha, J.A.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
• Texto Completo: http://hdl.handle.net/10773/37283
• topic: Advanced X-ray methods; High-resolution electron energy-loss spectroscopy; Anatase-rutile mixture; Apparent optical band gap; Visible-light

Titanium dioxide is by far the most used semiconductor material for photocatalytic applications. Still, it is transparent to visible-light. Recently, it has been proved that a type-II band alignment for the rutile − anatase mixture would improve visible-light absorption. In this research paper we thoroughly characterised the real crystalline and amorphous phases of synthesised titanias – thermally treated at different temperatures to get distinct ratios of anatase-rutile-amorphous fraction – as well as that of three commercially available photocatalytic nano-TiO2. Optical spectroscopy showed that even a small fraction of rutile (2 wt%) is able to shift to lower energies the apparent optical band gap of an anatase-rutile mixed phase. But is this enough to attain a real photocatalytic activity promoted by merely visible-light? We tried to give an answer to that question. Photocatalytic activity was assessed in the liquid- and gas-solid phase (employing rhodamine B and 4-chlorophenol, and isopropanol, respectively, as the organic substances to degrade) using a light source irradiating exclusively in the visible-range. Photocatalytic activity results in the liquid-solid phase showed that a high surface hydroxylation led to specimen with superior visible light-promoted catalytic activity – i.e. dye and ligand-to-metal charge transfer complexes sensitisation effects, not photocatalysis sensu-strictu. On the other hand, the gas-solid phase results showed that a higher amount of the absolute rutile fraction (around 10 wt%), together with less recombination of the charge carriers, were more effective for both visible-light absorption and a “real” visible-light promoted photocatalytic oxidation of isopropanol.