Visible light-active TiO₂ (m-TiO₂) nanoparticles were obtained by an electron beam treatment of commercial TiO₂ (p-TiO₂) nanoparticles. The m-TiO₂ nanoparticles exhibited a distinct red-shift in the UV-visible absorption spectrum and a much narrower band gap (2.85 eV) due to defects as confirmed by diffuse reflectance spectroscopy (DRS), photoluminescence (PL), X-ray diffraction, Raman spectroscopy, electron paramagnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS) and linear scan voltammetry (LSV). The XPS revealed changes in the surface states, composition, Ti⁴⁺ to Ti³⁺ ratio, and oxygen deficiencies in the m-TiO₂. The valence band XPS, DRS and PL results were carefully examined to understand the band gap reduction of m-TiO₂. The visible light-responsive enhanced photocatalytic activity of m-TiO₂ was demonstrated by degrading methylene blue and brilliant blue G. The EIS and LSV in the dark and under visible light irradiation further support the visible light-induced photocatalytic activities of the m-TiO₂ due to a decrease in electron transfer resistance and an increase in photocurrent. This study confirms that m-TiO₂ can be used effectively as a photocatalyst and photoelectrode material owing to its enhanced visible light-induced photocatalytic activity.

Energy level diagrams for undoped and N-doped TiO ₂ for visible light induced photocatalytic application.

Band gap narrowing is important and advantageous for potential visible light photocatalytic applications involving metal oxide nanostructures. This paper reports a simple biogenic approach for the promotion of oxygen vacancies in pure zinc oxide (p-ZnO) nanostructures using an electrochemically active biofilm (EAB), which is different from traditional techniques for narrowing the band gap of nanomaterials. The novel protocol improved the visible photocatalytic activity of modified ZnO (m-ZnO) nanostructures through the promotion of oxygen vacancies, which resulted in band gap narrowing of the ZnO nanostructure (E_g = 3.05 eV) without dopants. X-ray diffraction, UV-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy, Raman spectroscopy, photoluminescence spectroscopy and high resolution transmission electron microscopy confirmed the oxygen vacancy and band gap narrowing of m-ZnO. m-ZnO enhanced the visible light catalytic activity for the degradation of different classes of dyes and 4-nitrophenol compared to p-ZnO, which confirmed the band gap narrowing because of oxygen defects. This study shed light on the modification of metal oxide nanostructures by EAB with a controlled band structure.

An electrochemically active biofilm was utilized for modification of CeO₂nanostructures.