Toward a Visible Light-Driven Photocatalyst: The Effect of Midgap-States-Induced Energy Gap of Undoped TiO2 Nanoparticles

Abstract

TiO2 is one of the most promising candidate materials for clean-energy generation and environmental remediation. However, the larger-than 3.1 eV bandgap of perfectly crystalline TiO2 confines its application to the ultraviolet (UV) range. In this study, the electronic and the optical properties of undoped mixed-phase TiO2 nanoparticles were investigated using UV and inverse photoemission, low intensity X-ray photoelectron (XP), and diffused reflectance spectroscopy methods. The facile solution-phase synthesized nanoparticles exhibited a midgap-states-induced energy gap of only ∼2.2 eV. The diffused reflectance spectrum showed sub-bandgap absorption due to the existence of a large Urbach tail at 2.2 eV. The UV photoemission spectrum evidenced the presence of midgap states. The 2.2 eV energy gap enables the nanoparticles to be photoactive in the visible energy range. The gas-phase CO2 photoreduction test with water vapor under visible light illumination was studied in the presence of the synthesized TiO2 nanoparticles which resulted in the production of ∼1357 ppm gr-1(catalyst) CO and ∼360 ppm gr-1(catalyst) CH4, as compared to negligible amounts using a standard TiO2 (P25) sample. The synthesized nanoparticles possessed a Brunauer-Emmett-Teller (BET) surface area of ∼131 m2 gr-1, corresponding to a Langmuir surface area of ∼166 m2 gr-1. The determined interplanar distances of atomic planes by high-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) methods were consistent. A detailed elemental analysis using XPS and inductively coupled plasma mass spectrometry (ICP-MS) demonstrated that the synthesized catalyst is indeed undoped. The catalytic activity of the undoped synthesized nanoparticles in the visible spectrum can be ascribed to the unique electronic structure due to the presence of oxygen vacancy related defects and the high surface area. (Figure Presented).