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.

Child-centred design supported by comprehensive child application use analysis

Since children already use and explore applications on smartphones, we use this as the starting point for design. Our monitoring and analysis framework, BaranC, enables us to discover and analyse which applications children uses and precisely how they interact with them. The monitoring happens unobtrusively in the background so children interact normally in their own natural environment without artificial constraints. Thus, we can discover to what extent a child of a particular age engages with, and how they physically interact with, existing applications. This information in turn provides the basis for design of new child-centred applications which can then be subject to the same comprehensive child use analysis using our framework. The work focuses on the first aspect, namely, the monitoring and analysis of current child use of smartphones. Experiments show the value of this approach and interesting results have been obtained from this precise monitoring of child smartphone usage.