Reactivity of sub 1 nm supported clusters: (TiO2)(n) clusters supported on rutile TiO2 (110)

Metal oxide clusters of sub-nm dimensions dispersed on a metal oxide support are an important class of catalytic materials for a number of key chemical reactions, showing enhanced reactivity over the corresponding bulk oxide. In this paper we present the results of a density functional theory study of small sub-nm TiO2 clusters, Ti2O4, Ti3O6 and Ti4O8 supported on the rutile (110) surface. We find that all three clusters adsorb strongly with adsorption energies ranging from -3 eV to -4.5 eV. The more stable adsorption structures show a larger number of new Ti-O bonds formed between the cluster and the surface. These new bonds increase the coordination of cluster Ti and O as well as surface oxygen, so that each has more neighbours. The electronic structure shows that the top of the valence band is made up of cluster derived states, while the conduction band is made up of Ti 3d states from the surface, resulting in a reduction of the effective band gap and spatial separation of electrons and holes after photon absorption, which shows their potential utility in photocatalysis. To examine reactivity, we study the formation of oxygen vacancies in the cluster-support system. The most stable oxygen vacancy sites on the cluster show formation energies that are significantly lower than in bulk TiO2, demonstrating the usefulness of this composite system for redox catalysis.

Engineering of metal oxide interfaces for renewable energy applications

Diminishing non-renewable energy resources and planet-wide de-pollution on our planet are among the major problems which mankind faces into the future. To solve these problems, renewable energy sources such as readily available and inexhaustible sunlight will have to be used. There are however no readily available photocatalysts that are photocatalytically active under visible light; it is well established that the band gap of the prototypical photocatalyst, titanium dioxide, is the UV region with the consequence that only 4% of sun light is utilized. For this reason, this PhD project focused on developing new materials, based on titanium dioxide, which can be used in visible light activated photocatalytic hydrogen production and destruction of pollutant molecules. The main goal of this project is to use simulations based on first principles to engineer and understand rationally, materials based on modifying TiO2 that will have the following properties: (1) a suitable band gap in order to increase the efficiency of visible light absorption, with a gap around 2 – 2.5 eV considered optimum. (2). The second key aspect in the photocatalytic process is electron and hole separation after photoexcitation, which enable oxidation/reduction reactions necessary to i.e. decompose pollutants. (3) Enhanced activity over unmodified TiO2. In this thesis I present results on new materials based on modifying TiO2 with supported metal oxide nanoclusters, from two classes, namely: transition metal oxides (Ti, Ni, Cu) and p-block metal oxides (Sn, Pb, Bi). We find that the deposited metal oxide nanoclusters are stable at rutile and anatase TiO2 surfaces and present an analysis of changes to the band gap of TiO2, identifying those modifiers that can change the band gap to the desirable range and the origin of this. A successful collaboration with experimental researchers in Japan confirms many of the simulation results where the origin of improved visible light photocatalytic activity of oxide nanocluster-modified TiO2 is now well understood. The work presented in this thesis, creates a road map for the design of materials with desired photocatalytic properties and contributes to better understanding these properties which are of great application in renewable energy utilization.

Hybrid density functional theory description of N- and C-doping of NiO

The large intrinsic bandgap of NiO hinders its potential application as a photocatalyst under visible-light irradiation. In this study, we have performed first-principles screened exchange hybrid density functional theory with the HSE06 functional calculations of N- and C-doped NiO to investigate the effect of doping on the electronic structure of NiO. C-doping at an oxygen site induces gap states due to the dopant, the positions of which suggest that the top of the valence band is made up primarily of C 2p-derived states with some Ni 3d contributions, and the lowest-energy empty state is in the middle of the gap. This leads to an effective bandgap of 1.7 eV, which is of potential interest for photocatalytic applications. N-doping induces comparatively little dopant-Ni 3d interactions, but results in similar positions of dopant-induced states, i.e., the top of the valence band is made up of dopant 2p states and the lowest unoccupied state is the empty gap state derived from the dopant, leading to bandgap narrowing. With the hybrid density functional theory (DFT) results available, we discuss issues with the DFT corrected for on-site Coulomb description of these systems.

Isolating the photovoltaic junction: atomic layer deposited TiO2-RuO2 alloy Schottky contacts for silicon photoanodes

We synthesized nanoscale TiO2-RuO2 alloys by atomic layer deposition (ALD) that possess a high work function and are highly conductive. As such, they function as good Schottky contacts to extract photogenerated holes from n-type silicon while simultaneously interfacing with water oxidation catalysts. The ratio of TiO2 to RuO2 can be precisely controlled by the number of ALD cycles for each precursor. Increasing the composition above 16% Ru sets the electronic conductivity and the metal work function. No significant Ohmic loss for hole transport is measured as film thickness increases from 3 to 45 nm for alloy compositions >= 16% Ru. Silicon photoanodes with a 2 nm SiO2 layer that are coated by these alloy Schottky contacts having compositions in the range of 13-46% Ru exhibit average photovoltages of 525 mV, with a maximum photovoltage of 570 mV achieved. Depositing TiO2-RuO2 alloys on nSi sets a high effective work function for the Schottky junction with the semiconductor substrate, thus generating a large photovoltage that is isolated from the properties of an overlying oxygen evolution catalyst or protection layer.