Effect of doping on the photocatalytic, electronic and mechanical properties of sol-gel titanium dioxide films

Heterogeneous photocatalysis has been an active research area over the last decade as a promising solution for energy generation and environmental problems which has led to promising applications from air and water purification systems, self-cleaning and selfsterilizing surfaces to solar cells and hydrogen production from water dissociation reaction. Titanium dioxide (TiO2), an abundant material with a high photocatalytic efficiency and chemical stability, is undoubtedly the most widely studied and used among all photocatalytic materials. Although titanium dioxide has been used in powder form, its immobilized form (film) is necessary from practical application standpoint. However, there are several shortcomings of titanium dioxide films that need to be addressed to realize a wide range of successful applications: lack of visible light activity, poisoning of the catalytic performance by the substrate and the low surface area compared to powder forms. In addition, mechanical properties of such films have not been investigated thoroughly, which may be critical when abrasion and weathering resistance are necessary. To address each of these issues, a systematic experimental and theoretical investigation of doping titanium dioxide films with a variety of elementswere conducted. Utilizing theoretical calculations to filter elements for experimental studies as well as interpretation of the experimental results, several dopant or dopant combinations were found to remedy some of the issues of photocatalytic titanium dioxide films. Doping with 32 metals, nitrogen and 11 metal-nitrogen combinations are investigated theoretically and the results are used as guideline for the experimental studies. Particular attention is given to certain metal dopants such as Cr, V, Mo, Ta and Ga not just because of their relatively modest cost but also their non-toxicity and wide availability of their compatible compounds for sol-gel synthesis. While metal-dopants improved the overall efficiency and mechanical properties of titanium dioxide films, visible light activity is only achieved with nitrogen and metal-nitrogen doping where some of the metal co-dopants significantly improved the overall photocatalytic efficiency compared to nitrogen-only doped films. In addition, majority of the experimental studies is accompanied by nanoindentation technique to study the effect of doping and calcination on the key mechanicalproperties of titanium dioxide films. It is shown that good mechanical properties - good photocatalytic activity combinations can be achieved by a choice of appropriate dopant -dopant combinations and coupled with appropriate calcination parameters. Results of the theoretical and experimental investigations led to the development of first commercial photocatalytic tableware glass items which can be utilized under indoor lighting conditions by carefully selecting metal-nitrogen couples for doping of titanium dioxide films.