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.

Health of the older worker in Ireland - occupational physical and psychosocial factors in the autumn of work life

Introduction: Worldwide, governments are striving to keep people in work to an older age. However, little is known about the effects of work on an older workforce. This thesis aims to investigate the importance of job characteristics to the antecedents and evolution of cardiovascular disease and functional limitations for the older worker (50+ years). Methods: Three studies were used in this thesis. The 5C (Cork Coronary Care Case- Control) Study investigated the association between job strain and a coronary event in males (n=208) 35-74 years old. The Mitchelstown Study examined the association between job characteristics and positive lifestyle behaviours and further, job characteristics and blood pressure for males and females 50-69 years (n=2,047). Finally, the Cork & Kerry Study investigated the physical effects of manual work and reported functional limitations/disabilities in a sample of 60-80 year olds (n=362). Results: Results from the 5C Study show a clear difference between younger (<50 years) and older (≥50 years) workers, with older workers who had a coronary event more likely to have high job strain and low job control. Data from the Mitchelstown Study showed workers with intermediate possibility for development or high quantitative demands (versus low) at work significantly more likely to have co-occurrence of positive lifestyle behaviours. Further, those who had high possibility for development were more likely to have high systolic blood pressure with no indication of recovery from this activation at night. Physically demanding work as reported by the participants of the Cork & Kerry Study was associated with functional limitations and activities of daily living disability for both the paid and unpaid worker. Discussion: The findings from this piece of work highlight the necessity to examine job characteristics and health outcomes in isolation for the over fifties. The challenge is to get this information into the workplace.

The ways in which new public management ideas impact upon the administrative culture of 'street-level' bureaucrats and professionals working within Irish social policy

The conventional meaning of culture is ‘widely shared and strongly held values’ of a particular group or society (Bradley and Parker, 2006: 89). Culture is not a rigid concept; it can be influenced or altered by new ideas or forces. This research examines the ways in which one set of ideas in particular, that is, those associated with New Public Management, have impacted upon the administrative culture of 'street-level' bureaucrats and professionals within Irish social policy. Lipsky (1980: 3) defined 'street-level' bureaucrats as ‘public service workers who interact directly with citizens in the course of their jobs, and who have substantial discretion in the execution of their work’. Utilising the Competing Values Framework (CVF) in the analysis of eighty three semi-structured interviews with 'street-level' bureaucrats and professionals, an evaluation is made as to the impact of NPM ideas on both visible and invisible aspects of administrative culture. Overall, the influence of NPM is confined to superficial aspects of administrative culture such as; increased flexibility in working hours and to some degree job contracts; increased time commitment; and a customer service focus. However, the extent of these changes varies depending on policy sector and occupational group. Aspects of consensual and hierarchical cultures remain firmly in place. These coincide with features of developmental and market cultures. Contrary to the view that members of hierarchical and consensual culture would pose resistance to change, this research clearly illustrates that a very large appetite for change exists in the attitudes of 'street-level' bureaucrats and professionals within Irish social policy, with many of them suggesting changes that correspond to NPM ideas. This study demonstrates the relevance of employing the CVF model as it is clear that administrative culture is very much a dynamic system of competing and co-existing cultures.