Author ORCID Identifier

Date Available


Year of Publication


Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation




Chemical and Materials Engineering

First Advisor

Dr. Stephen E. Rankin


The optical and electronic properties of TiO2 thin films provide tremendous opportunities in several applications including photocatalysis, photovoltaics and photoconductors for energy production. Despite many attractive features of TiO2, critical challenges include the innate inability of TiO2 to absorb visible light and the fast recombination of photoexcited charge carriers. In this study, mesoporous TiO2 thin films are modified by doping using hydrogen and nitrogen, and sensitization using graphene quantum dot sensitization.

For all of these modifiers, well-ordered mesoporous titania films were synthesized by surfactant templated sol-gel process. Two methods: hydrazine and plasma treatments have been developed for nitrogen and hydrogen doping in the mesoporous titania films for band gap reduction, visible light absorption and enhancement of photocatalytic activity. The hydrazine treatment in mesoporous titania thin films suggests that hydrazine induced doping is a promising approach to enable synergistic incorporation of N and Ti3+ into the lattice of surfactant-templated TiO2 films and enhanced visible light photoactivity, but that the benefits are limited by gradual mesostructure deterioration. The plasma treated nitrogen doped mesoporous titania showed about 240 times higher photoactivity compared to undoped film in hydrogen production from photoelectrochemical water splitting under visible light illumination.

Plasma treated hydrogen doped mesoporous titania thin films has also been developed for enhancement of visible light absorption. Hydrogen treatment has been shown to turn titania (normally bright white) black, indicating vastly improved visible light absorption. The cause of the color change and its effectiveness for photocatalysis remain open questions. For the first time, we showed that a significant amount of hydrogen is incorporated in hydrogen plasma treated mesoporous titania films by neutron reflectometry measurements.

In addition to the intrinsic modification of titania by doping, graphene quantum dot sensitization in mesoporous titania film was also investigated for visible light photocatalysis. Graphene quantum dot sensitization and nitrogen doping of ordered mesoporous titania films showed synergistic effect in water splitting due to high surface area, band gap reduction, enhanced visible light absorption, and efficient charge separation and transport. This study suggests that plasma based doping and graphene quantum dot sensitization are promising strategies to reduce band gap and enhance visible light absorption of high surface area surfactant templated mesoporous titania films, leading to superior visible-light driven photoelectrochemical hydrogen production. The results demonstrate the importance of designing and manipulating the energy band alignment in composite nanomaterials for fundamentally improving visible light absorption, charge separation and transport, and thereby photoelectrochemical properties.

Digital Object Identifier (DOI)