Computational study of methyl derivatives of ammonia borane for hydrogen storage

The structures and thermodynamic properties of methyl derivatives of ammonia–borane (BH3NH3, AB) have been studied with the frameworks of density functional theory and second-order Møller–Plesset perturbation theory. It is found that, with respect to pure AB, methyl ammonia–boranes show higher complexation energies and lower reaction enthalpies for the release of H2, together with a slight increment of the activation barrier. These results indicate that the methyl substitution can enhance the reversibility of the system and prevent the formation of BH3/NH3, but no enhancement of the release rate of H2 can be expected.

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.

Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

Synthetic reevesite-like material as a visible light photocatalyst for the decontamination of water

A synthetic reevesite-like material has been shown to decolorize selected dyes and degrade phenolic contaminants photocatalytically in water when irradiated with visible light. This material can photoactively decolorize dyes such as bromophenol blue, bromocresol green, bromothymol blue, thymol blue and methyl orange in less than 15 min under visible light radiation in the absence of additional oxidizing agents. Conversely, phenolic compounds suc has phenol, p-chlorophenol and p-nitrophenol are photocat- alytically degraded in approximately 3hwith additional H2O2 when irradiated with visible light. These reactions offer potentially energy effective pathways for the removal of recalcitrant organic waste contaminants.

An approach for identifying the limit states of resilience of a water supply system

This paper presents an approach for identifying the limit states of resilience in a water supply system when influenced by different types of pressure (disturbing) forces. Understanding of systemic resilience facilitates identification of the trigger points for early managerial action to avoid further loss of ability to provide satisfactory service availability when the ability to supply water is under pressure. The approach proposed here is to illustrate the usefulness of a surrogate measure of resilience depicted in a three dimensional space encompassing independent pressure factors. That enables visualisation of the transition of the system-state (resilience) between high to low resilience regions and acts as an early warning trigger for decision-making. The necessity of a surrogate measure arises as a means of linking resilience to the identified pressures as resilience cannot be measured directly. The basis for identifying the resilience surrogate and exploring the interconnected relationships within the complete system, is derived from a meta-system model consisting of three nested sub-systems representing the water catchment and reservoir; treatment plant; and the distribution system and end-users. This approach can be used as a framework for assessing levels of resilience in different infrastructure systems by identifying a surrogate measure and its relationship to relevant pressures acting on the system.

Determination of vertical hydraulic conductivity of aquitards in a multilayered leaky system using water-level signals in adjacent aquifers

This paper presents a methodology for determining the vertical hydraulic conductivity (Kv) of an aquitard, in a multilayered leaky system, based on the harmonic analysis of arbitrary water-level fluctuations in aquifers. As a result, Kv of the aquitard is expressed as a function of the phase-shift of water-level signals measured in the two adjacent aquifers. Based on this expression, we propose a robust method to calculate Kv by employing linear regression analysis of logarithm transformed frequencies and phases. The frequencies, where the Kv are calculated, are identified by coherence analysis. The proposed methods are validated by a synthetic case study and are then applied to the Westbourne and Birkhead aquitards, which form part of a five-layered leaky system in the Eromanga Basin, Australia.

Safety enhancement of water-filled road safety barrier using interaction of composite materials

Road safety barriers are used to redirect traffic at roadside work-zones. When filled with water, these barriers are able to withstand low to moderate impact speeds up to 50kmh-1. Despite this feature, there are challenges when using portable water-filled barriers (PWFBs) such as large lateral displacements as well as tearing and breakage during impact, especially at higher speeds. In this study, the authors explore the use of composite action to enhance the crashworthiness of PWFBs and enable their use at higher speeds. Initially, we investigated the energy absorption capability of water in PWFB. Then, we considered the composite action of a PWFB with the introduction of a steel frame to evaluate its impact on performance. Findings of the study show that the initial height of impact must be lower than the free surface level of water in a PWFB for the water to provide significant crash energy absorption. In general, impact of a road barrier that is 80% filled is a good estimation. Furthermore, the addition of a composite structure greatly reduces the probability of tearing by decreasing the strain and impact energy transferred to the shell container. This allows the water to remain longer in the barrier to absorb energy via inertial displacement and sloshing response. Information from this research will aid in the design of next generation roadside safety structures aimed to increase safety on modern roadways.

Outsourcing data storage without outsourcing trust in cloud computing

The main theme of this thesis is to allow the users of cloud services to outsource their data without the need to trust the cloud provider. The method is based on combining existing proof-of-storage schemes with distance-bounding protocols. Specifically, cloud customers will be able to verify the confidentiality, integrity, availability, fairness (or mutual non-repudiation), data freshness, geographic assurance and replication of their stored data directly, without having to rely on the word of the cloud provider.

Smart coordination of energy storage units (ESUs) for voltage and loading management in distribution networks

This paper proposes a distributed control approach to coordinate multiple energy storage units (ESUs) to avoid violation of voltage and thermal constraints, which are some of the main power quality challenges for future distribution networks. ESUs usually are connected to a network through voltage source converters. In this paper, both ESU converters active and reactive power are used to deal with the above mentioned power quality issues. ESUs' reactive power is proposed to be used for voltage support, while the active power is to be utilized in managing network loading. Two typical distribution networks are used to apply the proposed method, and the simulated results are illustrated in this paper to show the effectiveness of this approach.

Insights into the mechanism of the reaction between ttrachloro-p-bnzoquinone and hydrogen peroxide and their implications in the catalytic role of water molecules in producing the hydroxyl radial

Detailed mechanisms for the formation of hydroxyl or alkoxyl radicals in the reactions between tetrachloro-p-benzoquinone (TCBQ) and organic hydroperoxides are crucial for better understanding the potential carcinogenicity of polyhalogenated quinones. Herein, the mechanism of the reaction between TCBQ and H2O2 has been systematically investigated at the B3LYP/6-311++G** level of theory in the presence of different numbers of water molecules. We report that the whole reaction can easily take place with the assistance of explicit water molecules. Namely, an initial intermediate is formed first. After that, a nucleophilic attack of H2O2 onto TCBQ occurs, which results in the formation of a second intermediate that contains an OOH group. Subsequently, this second intermediate decomposes homolytically through cleavage of the O-O bond to produce a hydroxyl radical. Energy analyses suggest that the nucleophilic attack is the rate-determining step in the whole reaction. The participation of explicit water molecules promotes the reaction significantly, which can be used to explain the experimental phenomena. In addition, the effects of F, Br, and CH3 substituents on this reaction have also been studied.

Experimental and numerical study of water-filled road safety barriers

Portable water-filled road barriers (PWFB) are roadside structures placed on temporary construction zones to separate work site from moving traffic. Recent changes in governing standards require PWFB to adhere to strict compliance in terms of lateral displacement of the road barriers and vehicle redirectionality. Actual road safety barrier test can be very costly, thus researchers resort to Finite Element Analysis (FEA) in the initial designs phase prior to real vehicle test. There has been many research conducted on concrete barriers and flexible steel barriers using FEA, however not many is done pertaining to PWFB. This research probes a new method to model joint mechanism in PWFB. Two methods to model the joining mechanism are presented and discussed in relation to its practicality and accuracy to real work applications. Moreover, the study of the physical gap and mass of the barrier was investigated. Outcome from this research will benefit PWFB research and allow road barrier designers better knowledge in developing the next generation of road safety structures.

Selecting rainfall events for effective Water Sensitive Urban Design (WSUD) implementation

The current approach for protecting the receiving water environment from urban stormwater pollution is the adoption of structural measures commonly referred to as Water Sensitive Urban Design (WSUD). The treatment efficiency of WSUD measures closely depends on the design of the specific treatment units. As stormwater quality can be influenced by rainfall characteristics, the selection of appropriate rainfall events for treatment design is essential to ensure the effectiveness of WSUD systems. Based on extensive field investigation of four urban residential catchments and computer modelling, this paper details a technically robust approach for the selection of rainfall events for stormwater treatment design using a three-component model. The modelling outcomes indicate that selecting smaller average recurrence interval (ARI) events with high intensity-short duration as the threshold for the treatment system design is the most feasible since these events cumulatively generate a major portion of the annual pollutant load compared to the other types of rainfall events, despite producing a relatively smaller runoff volume. This implies that designs based on small and more frequent rainfall events rather than larger rainfall events would be appropriate in the context of efficiency in treatment performance, cost-effectiveness and possible savings in land area needed.

Synthesis, characterisation and application of organic surfactants modified clays for water purification

This thesis offered a step forward in the development of cheap and effective materials for water treatment. It described the modification of naturally abundant clay minerals with organic molecules, and used the modified clays as effective adsorbents for the removal of recalcitrant organic water pollutants. The outcome of the study greatly extended our understanding of the synthesis and characteristic properties of clay and modified clay minerals, provided optimistic evaluation of the modified clays for environmental remediation and offered potential utility for clay minerals in the industry and environment.

Storage - the necessity for a Smart-Grid

Energy policy is driving renewable energy deployment with most of the developed countries having some form of renewable energy portfolio standard and emissions reduction target. To deliver upon these ambitious targets, those renewable energy technologies that are commercially available, such as wind and solar, are being deployed, but inherently have issues with intermittency of supply. To overcome these issues, storage options will need to be introduced into the distribution network with benefits for both demand management and power systems quality. How this can be utilised most effectively within the distribution network will allow for an even greater proportion of our energy demand to be met through renewable resources and meet the aspirational targets set. The distribution network will become a network of smart-grids, but to work efficiently and effectively, power quality issues surrounding intermittency must be overcome, with storage being a major factor in this solution.