Black Tio2 Nanomaterials For Energy Applications PDF Download

The exploration and application of nanomaterials have been attracting researchers' attention in recent decades. Nanocatalysts, as one of the very important classes of nanomaterials, have been developed for several generations. Nanotechnology makes light be possibly utilized in catalysis rather than only heat and allows multifunctional parts to be assembled in one catalyst. The TiO2 (as the representative of hetero-photocatalyst) and iron-based magnetic catalysts (as multifunctional catalyst) will be discussed in detail in this thesis. The first chapter will introduce the background of catalysts and nanomaterials. TiO2, especially black TiO2, will be mainly discussed in the aspects of properties, synthesis, and applications. Another part of the chapter will talk about the separation-friendly catalyst - magnetic heterogenous catalysts' synthesis and applications. Chapter 2 focuses on the synthetic route we used and the characterization of black TiO2 catalysts and magnetic catalysts. Both anatase and rutile black TiO2 catalysts were successfully prepared originally from Degussa P25 using the ethanol reduction method. The re-whitening treatment was also examined on both black TiO2 catalysts. All catalysts were characterized and compared by diffuse reflectance (DR), powder X-ray diffraction (XRD), and X-ray photoelectron spectroscope (XPS). Tauc plot results show that black TiO2 has smaller band gap than white TiO2. XPS revealed the existence of surface -OH species and Ti3+ in black TiO2. Furthermore, these two characterization techniques and XRD all proved that the blackening and re-whitening treatment does not change the crystalline phase of the catalysts, and the blackening treatment is reversible. For magnetic catalysts, we synthesized magnetic Fe2O3, Fe2O3@TiO2, copper/iron oxide magnetic TiO2, and black magnetic catalysts. Other than diffuse reflectance spectroscopy, Raman spectroscopy, scanning electron microscopy, and energy-dispersive X-ray elemental mapping analysis were used for determining the light-absorption properties, composition, and morphology of all synthesized magnetic catalysts. In addition, the magnetic separation was also achieved by simply applying an external magnetic field. Chapter 3 will discuss and compare the decarboxylation reaction activities of pristine, black, and re-whited TiO2 catalysts. The reactions were carried under the UV, blue, red, green, and white light irradiation. Unfortunately, the reaction was found only working under UV-light irradiation. The best solvent was dioxane which may be due to the proton affinity of the oxygen atom in dioxane molecule, which facilitates the deprotonation of the carboxylic acid. The optimal catalyst amount was found as 10 mg per 5 mL reaction mixture, and the kinetic study shows that the reaction is a pseudo-first order reaction. It is a pity that the performance of black TiO2 catalysts is worse than the pristine and re-whitened TiO2. Chapter 4 will talk about the sol-gel synthesized magnetic catalysts. These catalysts were used for aldehyde-alkyne-amine (A3) coupling reaction. The reaction was tested by light irradiating or traditional heating, but only heating can make the reaction proceed. Results also show that the coupling reaction requires copper to finish. The best solvent was found as toluene and the optimal reaction time is 6 hours at 120 ̊C. Sadly, the reactivity of copper/iron oxide magnetic TiO2 decreases a lot after three reaction cycles because of the copper leaching problem.