Involvement of incipient hydrous oxide species in electrocatalysis at some metal electrode surfaces

In this thesis a novel theory of electrocatalysis at metal (especially noble metal)/solution interfaces was developed based on the assumption of metal adatom/incipient hydrous oxide cyclic redox transitions. Adatoms are considered as metastable, low coverage species that oxidise in-situ at potentials of often significantly cathodic to the regular metal/metal oxide transition. Because the adatom coverage is so low the electrochemical or spectroscopic response for oxidation is frequently overlooked; however, the product of such oxidation, referred to here as incipient hydrous oxide seems to be the important mediator in a wide variety of electrocatalytically demanding oxidation processes. Conversely, electrocatalytically demanding reductions apparently occur only at adatom sites at the metal/solution interface - such reactions generally occur only at potentials below, i.e. more cathodic than, the adatom/hydrous oxide transition. It was established that while silver in base oxidises in a regular manner (forming initially OHads species) at potentials above 1.0 V (RHE), there is a minor redox transition at much lower potentials, ca. o.35 v (RHE). The latter process is assumed to an adatom/hydrous oxide transition and the low coverage Ag(l) hydrous oxide (or hydroxide) species was shown to trigger or mediate the oxidation of aldehydes, e. g. HCHO. The results of a study of this system were shown to be in good agreement with a kinetic model based on the above assumptions; the similarity between this type of behaviour and enzyme-catalysed processes - both systems involve interfacial active sites - was pointed out. Similar behaviour was established for gold where both Au(l) and Au(lll) hydrous oxide mediators were shown to be the effective oxidants for different organic species. One of the most active electrocatalytic materials known at the present time is platinum. While the classical view of this high activity is based on the concept of activated chemisorption (and the important role of the latter is not discounted here) a vital role is attributed to the adatom/hydrous oxide transition. It was suggested that the well known intermediate (or anomalous) peak in the hydrogen region of the cyclic voltanmogram for platinum region is in fact due to an adatom/hydrous oxide transition. Using potential stepping procedures to minimise the effect of deactivating (COads) species, it was shown that the onset (anodic sweep) and termination (cathodic sweep) potential for the oxidation of a wide variety of organics coincided with the potential for the intermediate peak. The converse was also shown to apply; sluggish reduction reactions, that involve interaction with metal adatoms, occur at significant rates only in the region below the hydrous oxide/adatom transition.

Becoming a father of a child with an intellectual disability- a narrative inquiry of Irish fathers’ stories

Background: This thesis explored men’s experiences of becoming a father of a child with an intellectual disability in the early years. In Ireland, it is estimated that there are almost 97% (n= 9,914) children with intellectual disabilities living at home in the care of parents, siblings, relatives or foster parents. While mothers and fathers are the primary caregivers, mothers’ experiences are well documented in comparison to the dearth of reports on fathers’ experiences. This descriptive narrative study aims to redress this gap in knowledge and understanding of men’s experiences of becoming a father of a child with an intellectual disability in the early years. Method: Narrative inquiry was employed for this study as it allows stories told by fathers to be collected as a means of exploring men’s transition to becoming a father of a child with an intellectual disability. A sample of 10 fathers of children with intellectual disabilities aged between thirteen months and five years of age were recruited from a large intellectual disability Health Service Provider (HSP) in the South of Ireland. Data were collected through semi-structured interviews which were audio-recorded, transcribed, and analysed using a narrative thematic approach. Findings: Findings are presented in four themes: i) ‘becoming a father’, ii) ‘something wrong with my child’, iii) ‘entering the world of disability’ and iv) ‘living a different life’. For all 10 fathers the time of being told that their child had an intellectual disability was laden with negative emotional responses irrespective of whether the diagnosis was at birth or more gradual over the child’s early developmental period. When fathers found out that ‘something was wrong’ they spoke of ‘moving on’ and entering the world of disability. In their narratives, becoming the father of a child with an intellectual disability had changed their lives and would inevitably change their futures. Fathers’ positivity was clearly evident with many fathers identifying that the diagnosis of their child with an intellectual disability was not a life ending event but rather a life changing event. Conclusions: Healthcare professionals have a critical role in supporting fathers during the transition to becoming a father of a child with an intellectual disability. Factors which require consideration include recognising that each father’s experience is unique; that fathers require support; and that fathers achieve personal growth because of their experiences of their transition to becoming a father of a child with an intellectual disability in the early years.