TiO2 and other titanium oxide-based nanomaterials have drawn immense attention from researchers in different scientific domains due to their fascinating multifunctional properties, relative abundance, environmental friendliness, and bio-compatibility. However, the physical and chemical properties of titanium oxide-based nanomaterials are found to be explicitly dependent on the presence of various crystal defects. Oxygen vacancies are the most common among them and have always been the subject of both theoretical and experimental research as they play a crucial role in tuning the inherent properties of titanium oxides. This review highlights different strategies for effectively introducing oxygen vacancies in titanium oxide-based nanomaterials, as well as a discussion on the positions of oxygen vacancies inside the TiO2 band gap based on theoretical calculations. Additionally, a detailed review of different experimental techniques that are extensively used for identifying oxygen vacancies in TiO2 nanostructures is also presented.

The formation and detection techniques of oxygen vacancies in titanium oxide-based nanostructures.

This paper describes the effects of defect distribution on energy band structure and the subsequent photocatalytic activity over TiO2 with exposed {001} facets as the model catalyst. Our results show that only surface oxygen vacancies (Vo’s) and Ti3+ centers in TiO2 can be induced by hydrogenation treatment, whereas the generation of bulk Vo’s and Ti3+ species depends on the thermal treatment in nitrogen. Both the surface and bulk defects in TiO2 can promote the separation of electron-hole pairs, enhance the light absorption, and increase the donor density. The presence of surface and bulk defects in TiO2 can not change the valence band maximum, but determine the conduction band minimum. Surface defects in TiO2 induce a tail of conduction band located above the H+/H2 redox potential, which benefits the photocatalytic performance. However, bulk defects in TiO2 generate a band tail below the H+/H2 potential, which inhibits hydrogen production. Thus, the change of band gap structure by defects is the major factor to determine the photocatalytic activity of TiO2 for hydrogen evolution. It is a new insight into the rational design and controllable synthesis of defect-engineered materials for various catalytic processes.

Insights into the Effects of Surface/Bulk Defects on Photocatalytic Hydrogen Evolution over TiO2 with Exposed {001} Facets

This paper reports a simple, biogenic and green approach to obtain narrow band gap and visible light-active TiO2 nanoparticles. Commercial white TiO2 (w-TiO2) was treated in the cathode chamber of a Microbial Fuel Cell (MFC), which produced modified light gray TiO2 (g-TiO2) nanoparticles. The DRS, PL, XRD, EPR, HR-TEM, and XPS were performed to understand the band gap decline of g-TiO2. The optical study revealed a significant decrease in the band gap of the g-TiO2 (E g  = 2.80 eV) compared to the w-TiO2 (E g  = 3.10 eV). The XPS revealed variations in the surface states, composition, Ti4+ to Ti3+ ratio, and oxygen vacancies in the g-TiO2. The Ti3+ and oxygen vacancy-induced enhanced visible light photocatalytic activity of g-TiO2 was confirmed by degrading different model dyes. The enhanced photoelectrochemical response under visible light irradiation further supported the improved performance of the g-TiO2 owing to a decrease in the electron transfer resistance and an increase in charge transfer rate. During the TiO2 treatment process, electricity generation in MFC was also observed, which was ~0.3979 V corresponding to a power density of 70.39 mW/m2. This study confirms narrow band gap TiO2 can be easily obtained and used effectively as photocatalysts and photoelectrode material.

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Microbial fuel cell assisted band gap narrowed TiO2 for visible light-induced photocatalytic activities and power generation.

Enhancement of visible-light photoactivity by polypropylene coated plasmonic Au/TiO 2 for dye degradation in water solution

Engineering oxygen-deficient ZrO2-x nanoplatform as therapy-activated “immunogenic cell death (ICD)” inducer to synergize photothermal-augmented sonodynamic tumor elimination in NIR-II biological window

G.M. Bhalerao

Papers

Influence of surface disorder, oxygen defects and bandgap in TiO2 nanostructures on the photovoltaic properties of dye sensitized solar cells