Increased charge transfer of Poly (ethylene oxide) based electrolyte by addition of small molecule and its application in dye-sensitized solar cells

A Poly (ethylene oxide) based polymer electrolyte impregnated with 2-Mercapto benzimidazole was comprehensively characterized by XRD, UV–visible spectroscopy, FTIR as well as electrochemical impedance spectroscopy. It was found that the crystallization of PEO was dramatically reduced and the ionic conductivity of the electrolyte was increased 4.5 fold by addition of 2-Mercapto benzimidazole. UV–visible and FTIR spectroscopes indicated the formation of charge transfer complex between 2-Mercapto benzimidazole and iodine of the electrolyte. Dye-sensitized solar cells with the polymer electrolytes were assembled. It was found that both the photocurrent density and photovoltage were enhanced with respect to the DSC without 2-Mercapto benzimidazole, leading to a 60% increase of the performance of the cell.

Hybrid graphene and graphitic carbon nitride nanocomposite : gap opening, electron–hole puddle, interfacial charge transfer, and enhanced visible light response

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C3N4) and electronically active graphene. We find an inhomogeneous planar substrate (g-C3N4) promotes electronrich and hole-rich regions, i.e., forming a well-defined electron−hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C3N4 substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C3N4 interface opens a 70 meV gap in g-C3N4-supported graphene, a feature that can potentially allow overcoming the graphene’s band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C3N4 is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C3N4 monolayer, the hybrid graphene/g-C3N4 complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

Hybrid graphene/titania nanocomposite : interface charge transfer, hole doping, and sensitization for visible light response

We demonstrated for the first time by large-scale ab initio calculations that a graphene/titania interface in the ground electronic state forms a charge-transfer complex due to the large difference of work functions between graphene and titania, leading to substantial hole doping in graphene. Interestingly, electrons in the upper valence band can be directly excited from graphene to the conduction band, that is, the 3d orbitals of titania, under visible light irradiation. This should yield well-separated electron−hole pairs, with potentially high photocatalytic or photovoltaic performance in hybrid graphene and titania nanocomposites. Experimental wavelength-dependent photocurrent generation of the graphene/titania photoanode demonstrated noticeable visible light response and evidently verified our ab initio prediction.

An influenza virus inspired polymer system for the timed release of siRNA

Small interfering RNA silences specific genes by interfering with mRNA translation, and acts to modulate or inhibit specific biological pathways; a therapy that holds great promise in the cure of many diseases. However, the naked small interfering RNA is susceptible to degradation by plasma and tissue nucleases and due to its negative charge unable to cross the cell membrane. Here we report a new polymer carrier designed to mimic the influenza virus escape mechanism from the endosome, followed by a timed release of the small interfering RNA in the cytosol through a self-catalyzed polymer degradation process. Our polymer changes to a negatively charged and non-toxic polymer after the release of small interfering RNA, presenting potential for multiple repeat doses and long-term treatment of diseases.

Charge-controlled switchable CO2 capture on boron nitride nanomaterials

Increasing concerns about the atmospheric CO2 concentration and its impact on the environment are motivating researchers to discover new materials and technologies for efficient CO2 capture and conversion. Here, we report a study of the adsorption of CO2, CH4, and H2 on boron nitride (BN) nanosheets and nanotubes (NTs) with different charge states. The results show that the process of CO2 capture/release can be simply controlled by switching on/off the charges carried by BN nanomaterials. CO2 molecules form weak interactions with uncharged BN nanomaterials and are weakly adsorbed. When extra electrons are introduced to these nanomaterials (i.e., when they are negatively charged), CO2 molecules become tightly bound and strongly adsorbed. Once the electrons are removed, CO2 molecules spontaneously desorb from BN absorbents. In addition, these negatively charged BN nanosorbents show high selectivity for separating CO2 from its mixtures with CH4 and/or H2. Our study demonstrates that BN nanomaterials are excellent absorbents for controllable, highly selective, and reversible capture and release of CO2. In addition, the charge density applied in this study is of the order of 1013 cm–2 of BN nanomaterials and can be easily realized experimentally.

Multicomponent charge transport in electrolyte solutions

The work presented in this thesis investigates the mathematical modelling of charge transport in electrolyte solutions, within the nanoporous structures of electrochemical devices. We compare two approaches found in the literature, by developing onedimensional transport models based on the Nernst-Planck and Maxwell-Stefan equations. The development of the Nernst-Planck equations relies on the assumption that the solution is infinitely dilute. However, this is typically not the case for the electrolyte solutions found within electrochemical devices. Furthermore, ionic concentrations much higher than those of the bulk concentrations can be obtained near the electrode/electrolyte interfaces due to the development of an electric double layer. Hence, multicomponent interactions which are neglected by the Nernst-Planck equations may become important. The Maxwell-Stefan equations account for these multicomponent interactions, and thus they should provide a more accurate representation of transport in electrolyte solutions. To allow for the effects of the electric double layer in both the Nernst-Planck and Maxwell-Stefan equations, we do not assume local electroneutrality in the solution. Instead, we model the electrostatic potential as a continuously varying function, by way of Poisson’s equation. Importantly, we show that for a ternary electrolyte solution at high interfacial concentrations, the Maxwell-Stefan equations predict behaviour that is not recovered from the Nernst-Planck equations. The main difficulty in the application of the Maxwell-Stefan equations to charge transport in electrolyte solutions is knowledge of the transport parameters. In this work, we apply molecular dynamics simulations to obtain the required diffusivities, and thus we are able to incorporate microscopic behaviour into a continuum scale model. This is important due to the small size scales we are concerned with, as we are still able to retain the computational efficiency of continuum modelling. This approach provides an avenue by which the microscopic behaviour may ultimately be incorporated into a full device-scale model. The one-dimensional Maxwell-Stefan model is extended to two dimensions, representing an important first step for developing a fully-coupled interfacial charge transport model for electrochemical devices. It allows us to begin investigation into ambipolar diffusion effects, where the motion of the ions in the electrolyte is affected by the transport of electrons in the electrode. As we do not consider modelling in the solid phase in this work, this is simulated by applying a time-varying potential to one interface of our two-dimensional computational domain, thus allowing a flow field to develop in the electrolyte. Our model facilitates the observation of the transport of ions near the electrode/electrolyte interface. For the simulations considered in this work, we show that while there is some motion in the direction parallel to the interface, the interfacial coupling is not sufficient for the ions in solution to be "dragged" along the interface for long distances.

Role of charge in destabilizing AlH4 and BH4 complex anions for hydrogen storage applications : Ab initio density functional calculations

NaAlH4 and LiBH4 are potential candidate materials for mobile hydrogen storage applications, yet they have the drawback of being highly stable and desorbing hydrogen only at elevated temperatures. In this letter, ab initio density functional theory calculations reveal how the stabilities of the AlH4 and BH4 complex anions will be affected by reducing net anionic charge. Tetrahedral AlH4 and BH4 complexes are found to be distorted with the decrease of negative charge. One H-H distance becomes smaller and the charge density will overlap between them at a small anion charge. The activation energies to release of H2 from AlH4 and BH4 complexes are thus greatly decreased. We demonstrate that point defects such as neutral Na vacancies or substitution of a Na atom with Ti on the NaAlH4(001) surface can potentially cause strong distortion of neighboring AlH4 complexes and even induce spontaneous dehydrogenation. Our results help to rationalize the conjecture that the suppression of charge transfer to AlH4 and BH4 anion as a consequence of surface defects should be very effective for improving the recycling performance of H2 in NaAlH4 and LiBH4. The understanding gained here will aid in the rational design and development of hydrogen storage materials based on these two systems.

Does residential dissonance impact residential mobility?

This research identifies residential mobility behaviour impacts of residential dissonance in Transit Oriented Developments (TODs) vs. non-TODs in Brisbane, Australia. Based on the characteristics of living environments (density, diversity, connectivity, and accessibility) and the travel preferences of 4545 individuals, respondents in 2009 were classified into one of four categories including: TOD consonants, TOD dissonants, non-TOD dissonants, and non-TOD consonants. Binary logistic regression analyses were employed to identify residential mobility behaviour of groups between 2009 and 2011; controlling for time varying covariates. The findings show that both TOD dissonants and TOD consonants move residences at an equal rate. However, TOD dissonants are more likely to move residences to their preferred non-TOD areas. In contrast, non-TOD dissonants not only moved residences at a lower rate, but their rate of mobility to their preferred TOD neighbourhood is also significantly lower due to costs and other associated factors. The findings suggest that discrete land use policy development is required to integrate non-TOD dissonant and TOD dissonant behaviours to support TOD development in Brisbane.

Job changes, occupational mobility and human capital acquisition : an empirical analysis

Most individuals have more than one job or occupation in their working lives. Most employees are repeatedly faced with the choice of whether to remain in their present job (with the possibility of promotion), or quit to another job in the same occupation with a different firm, or - more radically change occupation. At each stage in an individual's career, the scope for future job or occupational mobility is largely conditioned by the type and quantity of their human capital. This paper presents an empirical study of the factors which link occupational mobility and the acquisition of either firm-based, occupation-specific or general human capital. The data employed are from a cohort of 1980 UK graduates drawn from the Department of Employment Survey 1987. The econometric work presents estimates of the role of firm-based training and occupation-specific training in the career mobility of qualified manpower in the first seven years in the labour market

Harmonic quality of multilevel cascade inverters with random carrier phase pulse width modulation

The output harmonic quality of N series connected full-bridge dc-ac inverters is investigated. The inverters are pulse width modulated using a common reference signal but randomly phased carrier signals. Through analysis and simulation, probability distributions for inverter output harmonics and vector representations of N carrier phases are combined and assessed. It is concluded that a low total harmonic distortion is most likely to occur and will decrease further as N increases.

The journey of becoming involved : the experience of participation in urban spaces by children with diverse mobility

Despite considerable discussion regarding the virtues of participation in urban spaces, the urban experience of children with disabilities has been largely ignored. This intensive study reported on the everyday experience of urban participation on the part of children with conditions such as cerebral palsy, muscular dystrophy, and juvenile arthritis, contributing new insights into their experience of journeys central to becoming involved in settings such as schools, neighbourhoods and shopping centres. The study identified problems in body – space – context relationships as points of intervention in our urban settings that promise to make a significant difference to their everyday journeys.

NSAM-derived total surface area vs. SMPS-derived "mobility equivalent" surface area for different environmentally relevant aerosols

The surface area of inhaled particles deposited in the alveolar region, as reported by the TSI nanoparticle surface area monitor (NSAM), was compared with the corresponding value estimated by a TSI scanning mobility particle sizer (SMPS) for a range of environmentally relevant aerosols, including petrol emissions, ETS, laser printer emissions, cooking emissions and ambient aerosols. The SMPS values were based on a mobility size distribution assuming spherical particles using the appropriate size-dependent alveolar-deposition factors provided by the ICRP. In most cases, the two instruments showed good linear agreement. With petrol emissions and ETS, the linearity extended to over 103 μm2 cm-3. With printer emissions, there was good linearity up to about 300 μm2 cm-3 while the NSAM increasingly overestimated the surface area at higher concentrations. The presence of a nucleation event in ambient air caused the NSAM to over-estimate the surface area by a factor of 2. We summarize these results and conclude that the maximum number concentration up to which the NSAM is accurate clearly depends on the type of aerosol being sampled and provide guidance for the use of the instrument.

Application of kaolin amorphous derivative as a nitrogen carrier

Sandy soils have low nutrient holding capacity and high water conductivity. Consequently, nutrients applied as highly soluble chemical fertilisers are prone to leaching, particularly in heavily irrigated environments such as horticultural soils and golf courses. Amorphous derivatives of kaolin with high cation exchange capacity may be loaded with desired nutrients and applied as controlledrelease fertilisers. Kaolin is an abundant mineral, which can be converted to a meso-porous amorphous derivative (KAD) using facile chemical processes. KAD is currently being used to sequester ammonium from digester effluent in sewage treatment plants in a commercial environment. This material is also known in Australia by the trade name MesoLite. The ammonium-saturated form of KAD may be applied to soils as a nitrogen fertiliser. Up to 7% N can be loaded onto KAD by contacting it with high-ammonia concentration wastewater from sewerage treatment plants. This poster paper demonstrates plant uptake of nitrogen from KAD and compares its efficiency as a fertiliser with NH4SO4. Rye grass was grown in 1kg pots in a glass-house. Nitrogen was applied at a range of rates using NH4SO4 and two KAD materials carrying 7% and 3% nitrogen, respectively. All other nutrients were applied in adequate amounts. All treatments were replicated three times. Plants were harvested after four weeks. Dry mass and N concentrations were determined by standard methods. At all N application rates, ammonium-loaded KAD produced significantly higher plant mass than for NH4SO4. The lower fertiliser effectiveness of NH4SO4 is attributed to possible loss of some N through volatilisation. Of the two KAD types, the material with lower CEC value supported slightly higher plant yields. The KAD materials did not show any adverse effect on availability of trace elements, as evidenced by lack of deficiency symptoms and plant analyses. Clearly, nitrogen loaded on to KAD in the form of ammonium is likely to be protected from leaching, but is still available to plants. These data suggest that KAD-based fertilisers may be suitable substitutes for water soluble N, K and other cation fertilisers for leaching soils.

Harmonic quality of multilevel cascade inverters with random carrier phase pulse width modulation

The output harmonic quality of N series connected full-bridge dc-ac inverters is investigated. The inverters are pulse width modulated using a common reference signal but randomly phased carrier signals. Through analysis and simulation, probability distributions for inverter output harmonics and vector representations of N carrier phases are combined and assessed. It is concluded that a low total harmonic distortion is most likely to occur and will decrease further as N increases.

Older people's mobility within the community : the impact of built environment and transportation on active aging

Population ageing is one of the major challenges of the 21st century and societies need to optimize opportunities for active ageing. This thesis explored how the built environment impacts the mobility and participation within the community. A combination of person-based GPS tracking and in-depth interviews was used to collect data on transportation use and engagement in activities of older people living within Brisbane. It showed that the built environment has a strong impact on mobility. To enable healthy and active ageing modern communities need to overcome car dependency and provide mobility options that are tailored towards older people’s needs.