Continuous hydrothermal flow synthesis of nanoceramics for photocatalytic and microwave dielectric applications

Abstract

TiO2 is widely considered as a promising photocatalyst to degrade various organic pollutants in water, and to harvest sunlight renewable energy application. However, the efficiency of the photocatalytic reaction using TiO2 is not high due to its wide band-gap (3.22 eV, corresponding to the wavelength of 385 nm), which corresponds to the lower end of the wavelengths of solar light. The aim of this project is to use a continuous hydrothermal flow synthesis (CHFS) technique and other post-treatment methods to synthesize and tailor nano-TiO2 and TiO2-related photocatalysts for improved photoactivity. It was demonstrated that the rapid crystallising environment in a CHFS system resulted in the anatase phase of TiO2 (ca. 5 nm) with a high surface area and a high crystallinity. The CHFS system provides a flexible route of doping TiO2 at the atomic level (lattice doping) either to decrease the band-gap or to introduce intra-band gap states, which allow activation by visible-light. The structures of the resulting nanocatalysts were investigated using powder X-ray diffraction (XRD) and Raman spectroscopy. The quantity and chemical nature of the catalyst surface were determined by X-ray photoelectron spectroscopy (XPS). Morphologies of the products were characterized by Transmission Electron Spectroscopy (TEM) and Scanning Electron Spectroscopy (SEM). Band-gap energy was determined by UV-Vis spectrophotometry. A TiO2-CeO2 composite catalyst was successfully synthesized by CHFS. A stable solid-solution was indentified, which leads to a totally different optical property (i.e. with a narrow band-gap) when mixed with a methylene blue (MB) dye solution. All the composites materials show improved photodecolourisation rates. Novel 2D sodium titanate nano-sheets (ca. 400×500 nm) were developed with a high concentration of NaOH into the reactor. This material exhibits the highest photocatalytic efficiency amongst all materials being tested in this project. Several post-treatment methods were also adopted to further modify the CHFS-prepared nano-TiO2 samples. By heat-treating nano-TiO2 powder in air, the crystallinity of the sample was increased. By exposing the nano-TiO2 to ammonia atmosphere at a range of temperatures, products ranging from N-doped anatase TiO2 to phase-pure titanium nitride (TiN) were successfully obtained. N-doped TiO2 materials showed significant red-shift in band-gap. Surface modification of TiO2 in vanadium salt leads to a high surface absorbability and photo-oxidising power. Among all the modified samples, some of them indeed exhibited improved photocatalytic activity over the unmodified nano-TiO2. Moreover, the microwave dielectric properties of selected TiO2 samples (metal ion lattice doped) were also examined using sintered TiO2 discs. The results suggest that a useful dielectric resonator material can be achieved by introduction of certain dopants in combination with a spark plasma sintering (SPS) method.