Dinuclear Ru-Cu complexes : electronic characterisation and application to dye-sensitised solar cells

Dye-sensitised solar cells have emerged as an important developing technology for low-cost solar energy conversion and a crucial element of these is the dye, responsible for light harvesting and control of interfacial electron-transfer processes.[1] A number of examples of dye exist in the literature which link a ruthenium polypyridyl complex to another platinum group metal complex such as Ru (II), Os (II), Re (I) or Rh (III) via a bridging ligand.[2-6] These systems are often referred to as heterosupramolecular triads when adsorbed on the surface of TiO2 as the semiconductor becomes an active component in the system. A number of problems can arise with these types of sensitisers, for example if a flexible linker, e.g. bis-pyridylethane, is used to couple the two complexes it can be hard to control the orientation of the whole dye. This may lead to the resultant dye cation hole being closer to the surface than desired, and hence the long-lived charge-separated state is not achieved. In addition the size of these dyes may be much larger than that of a mononuclear complex and can lead to poor pore filling on the TiO2 and lower dye coverage, leading to a lower efficiency cell.[7] Despite these issues, efficient charge-separation has been achieved with polynuclear complexes and a long-lived state on the millisecond timescale has been observed for a trinuclear ruthenium complex.[8]

Kinetics of electron recombination of dye-senitized solar cells based on TiO2 nanorod arrays sensitized with different dyes

The performance and electron recombination kinetics of dye-sensitized solar cells based on TiO2 films consisting of one-dimensional nanorod arrays (NR-DSSCs) which are sensitized with dye N719, C218 and D205 respectively have been studied. It has been found that the best efficiency is obtained with the dye C218 based NR-DSSCs, benefiting from a 40% higher short-circuit photocurrent density. However, the open circuit photovoltage of the N719 based cell is 40 mV higher than that of the organic dye C218 and D205 based devices. Investigation of the electron recombination kinetics of the NR-DSSCs has revealed that the effective electron lifetime, τn, of the N719 based NR-DSSC is the lowest whereas the τn of the C218 based NR-DSSC is the highest among the three dyes. The higher Voc with the N719 based NR-DSSC is originated from the more negative energy level of the conduction band of the TiO2 film. In addition, in comparison to the DSSCs with conventional nanocrystalline particles based TiO2 films, the NR-DSSCs have shown over two orders of magnitude higher τn when employing N719 as the sensitizer. Nevertheless, the τn of the DSSCs with the C218 based nanorod arrays is only ten-fold higher than the that of the nanoparticles based devices. The remarkable characteristic of the dye C218 in suppressing the electron recombination of DSSCs is discussed.

The motivation and structure of corrupt police networks : theorising the dark side of the ‘thin blue line’

In recent times considerable research attention has been directed to understanding dark networks, especially criminal and terrorist networks. Dark networks are those in which member motivations are self rather than public interested, achievements come at the cost of other individuals, groups or societies and, in addition, their activities are both ‘covert and illegal’ (Raab & Milward, 2003: 415). This ‘darkness’ has implications for the way in which these networks are structured, the strategies adopted and their recruitment methods. Such entities exhibit distinctive operating characteristics including most notably the tension between creating an efficient network structure while retaining the ability to hide from public view while avoiding catastrophic collapse should one member cooperate with authorities (Bouchard 2007). While theoretical emphasis has been on criminal and terrorist networks, recent work has demonstrated that corrupt police networks exhibit some distinctive characteristics. In particular, these entities operate within the shadows of a host organisation - the Police Force and distort the functioning of the ‘Thin Blue Line’ as the interface between the law abiding citizenry and the criminal society. Drawing on data derived from the Queensland Fitzgerald Commission of Enquiry into Police Misconduct and related documents, this paper examines the motivations, structural properties and operational practices of corrupt police networks and compares and contrasts these with other dark networks with ‘bright’ public service networks. The paper confirms the structural differences between dark corrupt police networks and bright networks and suggests. However, structural embeddedness alone is found to be an insufficient theoretical explanation for member involvement in networks and that a set of elements combine to impact decision-making. Although offering important insights into network participation, the paper’s findings are especially pertinent in identifying additional points of intervention for police corruption networks.

Deep Blue Orchestra

Under an Australian Research Council Linkage Grant, the partnering research organisations QUT, Creative Media Warehouse, The Brisbane Festival and The Queensland Orchestra undertook extensive reviews of many aspects of traditional and contemporary arts practice. We will publish excerpts from the findings soon. deepblue is committed to ongoing research as a part of the day to day operation and is currently working in partnership with John Kotzas and the team at QPAC on exploring new techniques for presenting and marketing deep blue.

Reduced electron recombination of dye-sensitized solar cells based on TiO 2 spheres consisting of ultrathin nanosheets with [001] facet exposed

An anatase TiO 2 material with hierarchically structured spheres consisting of ultrathin nanosheets with 100% of the [001] facet exposed was employed to fabricate dye-sensitized solar cells (DSC s). Investigation of the electron transport and back reaction of the DSCs by electrochemical impedance spectroscopy showed that the spheres had a threefold lower electron recombination rate compared to the conventional TiO 2 nanoparticles. In contrast, the effective electron diffusion coefficient, D n, was not sensitive to the variation of the TiO 2 morphology. The TiO 2 spheres showed the same Dn as that of the nanoparticles. The influence of TiCl 4 post-treatment on the conduction band of the TiO 2 spheres and on the kinetics of electron transport and back reactions was also investigated. It was found that the TiCl 4 post-treatment caused a downward shift of the TiO 2 conduction band edge by 30 meV. Meanwhile, a fourfold increase of the effective electron lifetime of the DSC was also observed after TiCl4 treatment. The synergistic effect of the variation of the TiO 2 conduction band and the electron recombination determined the open-circuit voltage of the DSC. © 2012 Wang et al.

Computational design of cyclic nitroxides as efficient redox mediators for dye-sensitized solar cells

Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E° ox and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Validation of a food behavior questionnaire for male blue collar workers

During nutrition intervention programs, some form of dietary assessment is usually necessary. This dietary assessment can be for: initial screening; development of appropriate programs and activities; or, evaluation. Established methods of dietary assessment are not always practical, nor cost effective in such interventions, therefore an abbreviated dietary assessment tool is needed. The Queensland Nutrition Project developed such a tool for male Blue Collar Workers, the Food Behaviour Questionnaire, consisting of 27 food behaviour related questions. This tool has been validated in a sample of 23 men, through full dietary assessment obtained via food frequency questionnaires and 24 hour dietary recalls. Those questions which correlated poorly with the full dietary assessment were deleted from the tool. In all, 13 questions was all that was required to distinguish between high and low dietary intakes of particular nutrients. Three questions when combined had correlations with refined sugar between 0.617 and 0.730 (p<0.005); four questions when combined had correlations with dietary fibre as percentage of energy of 0.45 (p<0.05); five questions when combined had a correlation with total fat of 0.499 (p<0.05); and, 4 questions when combined had a correlation with saturated fat of between 0.451 and 0.589 (p<0.05). A significant correlation could not be found for food behaviour questions with respect to dietary sodium. Correlations for fat as a function of energy could not be found.

Between the Devil and the Deep-blue Sea: Conceptualizing Victims Experiences of Policing in Domestic Violence in the Singaporean Context

In contextualising victims' experiences of policing in domestic violence situations in Singapore, two extreme but interrelated sets of responses have been observed. At one end of the continuum, criminal justice sanctions are strictly contingent upon victim willingness to initiate criminal proceedings against the perpetrator, and at the other, victims' rights, needs and preferences seem to be usurped by the justice system regardless of victims' choice. Neither of these positions takes victims' interests into account. Nor do they stem from an understanding of the sociocultural, economic and structural circumstances in which victims experienced violence, and continued to experience it, long after a police intervention. Data from the research revealed that criminalisation as an ideological and legally practical tool was not only rendered ineffective but irrelevant to the experiences of women in the Singaporean context.Two factors account for this phenomenon. First, the absence of support structures to achieve criminalisation and address victims' needs in the aftermath of criminalisation; second, the authoritative, paternalistic and patriarchal state impedes processes aimed at the empowerment of women victims.