Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

Exploring the relationship between patterns of physical activity, sedentary behaviour and cardiometabolic health in middle-aged Irish adults

Background and Study Rationale Being physically active is a major contributor to both physical and mental health. More specifically, being physically active lowers risk of coronary heart disease, high blood pressure, stroke, metabolic syndrome (MetS), diabetes, certain cancers and depression, and increases cognitive function and wellbeing. The physiological mechanisms that occur in response to physical activity and the impact of total physical activity and sedentary behaviour on cardiometabolic health have been extensively studied. In contrast, limited data evaluating the specific effects of daily and weekly patterns of physical behaviour on cardiometabolic health exist. Additionally, no other study has examined interrelated patterns and minute-by-minute accumulation of physical behaviour throughout the day across week days in middle-aged adults. Study Aims The overarching aims of this thesis are firstly to describe patterns of behaviour throughout the day and week, and secondly to explore associations between these patterns and cardiometabolic health in a middle-aged population. The specific objectives are to: 1 Compare agreement between the International Physical Activity Questionnaire-Short Form (IPAQ-SF) and GENEActiv accelerometer-derived moderate-to-vigorous (MVPA) activity and secondly to compare their associations with a range of cardiometabolic and inflammatory markers in middle-aged adults. 2 Determine a suitable monitoring frame needed to reliably capture weekly, accelerometer-measured, activity in our population. 3 Identify groups of participants who have similar weekly patterns of physical behaviour, and determine if underlying patterns of cardiometabolic profiles exist among these groups. 4 Explore the variation of physical behaviour throughout the day to identify whether daily patterns of physical behaviour vary by cardiometabolic health. Methods All results in this thesis are based on data from a subsample of the Mitchelstown Cohort; 475 (46.1% males; mean aged 59.7±5.5 years) middle-aged Irish adults. Subjective physical activity levels were assessed using the IPAQ-SF. Participants wore the wrist GENEActiv accelerometer for 7 consecutive days. Data was collected at 100Hz and summarised into a signal magnitude vector using 60s epochs. Each time interval was categorised based on validated cut-offs. Data on cardiometabolic and inflammatory markers was collected according to standard protocol. Cardiometabolic outcomes (obesity, diabetes, hypertension and MetS) were defined according to internationally recognised definitions by World Health Organisation (WHO) and Irish Diabetes Federation (IDF). Results The results of the first chapter suggest that the IPAQ-SF lacks the sensitivity to assess patterning of activity and guideline adherence and assessing the relationship with cardiometabolic and inflammatory markers. Furthermore, GENEActiv accelerometer-derived MVPA appears to be better at detecting relationships with cardiometabolic and inflammatory markers. The second chapter examined variations in day-to-day physical behaviour levels between- and within-subjects. The main findings were that Sunday differed from all other days in the week for sedentary behaviour and light activity and that a large within-subject variation across days of the week for vigorous activity exists. Our data indicate that six days of monitoring, four weekdays plus Saturday and Sunday, are required to reliably estimate weekly habitual activity in all activity intensities. In the next chapter, latent profile analysis of weekly, interrelated patterns of physical behaviour identified four distinct physical behaviour patterns; Sedentary Group (15.9%), Sedentary; Lower Activity Group (28%), Sedentary; Higher Activity Group (44.2%) and a Physically Active Group (11.9%). Overall the Sedentary Group had poorer outcomes, characterised by unfavourable cardiometabolic and inflammatory profiles. The remaining classes were characterised by healthier cardiometabolic profiles with lower sedentary behaviour levels. The final chapter, which aimed to compare daily cumulative patterns of minute-by-minute physical behaviour intensities across those with and without MetS, revealed significant differences in weekday and weekend day MVPA. In particular, those with MetS start accumulating MVPA later in the day and for a shorted day period. Conclusion In conclusion, the results of this thesis add to the evidence base regards an optimal monitoring period for physical behaviour measurement to accurately capture weekly physical behaviour patterns. In addition, the results highlight whether weekly and daily distribution of activity is associated with cardiometabolic health and inflammatory profiles. The key findings of this thesis demonstrate the importance of daily and weekly physical behaviour patterning of activity intensity in the context of cardiometabolic health risk. In addition, these findings highlight the importance of using physical behaviour patterns of free-living adults observed in a population-based study to inform and aid health promotion activity programmes and primary care prevention and treatment strategies and development of future tailored physical activity based interventions.