A density functional theory study on CO2 capture and activation by graphene-like boron nitride with boron vacancy

First principle calculations for a hexagonal (graphene-like) boron nitride (g-BN) monolayer sheet in the presence of a boron-atom vacancy show promising properties for capture and activation of carbon dioxide. CO2 is found to decompose to produce an oxygen molecule via an intermediate chemisorption state on the defect g-BN sheet. The three stationary states and two transition states in the reaction pathway are confirmed by minimum energy pathway search and frequency analysis. The values computed for the two energy barriers involved in this catalytic reaction after enthalpy correction indicate that the catalytic reaction should proceed readily at room temperature.

Vacancy mediated desorption of hydrogen from a sodium alanate surface : An ab initio spin-polarized study

Ab initio spin-polarized density functional theory calculations are performed to explore the effect of single Na vacancy on NaAlH4(001) surface on the initial dehydrogenation kinetics. The authors found that two Al–H bond lengths become elongated and weakened due to the presence of a Na vacancy on the NaAlH4(001) surface. Spontaneous recombination from the surface to form molecular hydrogen is observed in the spin-polarized ab initio molecular dynamics simulation. The authors’ results indicate that surface Na vacancies play a critical role in accelerating the dehydrogenation kinetics in sodium alanate. The understanding gained here will aid in the rational design and development of complex hydride materials for hydrogen storage

Suppressed thermal conductivity of bilayer graphene with vacancy-initiated linkages

Through larger-scale molecular dynamics simulations, we investigated the impacts from vacancy-initiated linkages on the thermal conductivity of bilayer graphene sheets (of size L × W = 24.5 nm × 3.7 nm). Three different interlayer linkages, including divacancy bridging, “spiro” interstitial bridging and Frenkel pair defects, are considered. It is found that the presence of interlayer linkages induces a significant degradation in the thermal conductivity of the bilayer graphene sheet. The degradation is strongly dependent on the interlayer linkage type, concentration and location. More importantly, the linkages that contain vacancies lead to more severe suppression of the thermal conductivity, in agreement with theoretical predictions that vacancies induce strong phonon scattering. Our finding provides useful guidelines for the application of multilayer graphene sheets in practical thermal management.

Risk-assessment practices in the private rental sector : implications for low-income renters (Final Report)

This report focuses on risk-assessment practices in the private rental market, with particular consideration of their impact on low-income renters. It is based on the fieldwork undertaken in the second stage of the research process that followed completion of the Positioning Paper. The key research question this study addressed was: What are the various factors included in ‘risk-assessments’ by real estate agents in allocating ‘affordable’ tenancies? How are these risks quantified and managed? What are the key outcomes of their decision-making? The study builds on previous research demonstrating that a relatively large proportion of low-cost private rental accommodation is occupied by moderate- to high-income households (Wulff and Yates 2001; Seelig 2001; Yates et al. 2004). This is occurring in an environment where the private rental sector is now the de facto main provider of rental housing for lower-income households across Australia (Seelig et al. 2005) and where a number of factors are implicated in patterns of ‘income–rent mismatching’. These include ongoing shifts in public housing assistance; issues concerning eligibility for rent assistance; ‘supply’ factors, such as loss of low-cost rental stock through upgrading and/or transfer to owner-occupied housing; patterns of supply and demand driven largely by middle- to high-income owner-investors and renters; and patterns of housing need among low-income households for whom affordable housing is not appropriate. In formulating a way of approaching the analysis of ‘risk-assessment’ in rental housing management, this study has applied three sociological perspectives on risk: Beck’s (1992) formulation of risk society as entailing processes of ‘individualisation’; a socio-cultural perspective which emphasises the situated nature of perceptions of risk; and a perspective which has drawn attention to different modes of institutional governance of subjects, as ‘carriers of specific indicators of risk’. The private rental market was viewed as a social institution, and the research strategy was informed by ‘institutional ethnography’ as a method of enquiry. The study was based on interviews with property managers, real estate industry representatives, tenant advocates and community housing providers. The primary focus of inquiry was on ‘the moment of allocation’. Six local areas across metropolitan and regional Queensland, New South Wales, and South Australia were selected as case study localities. In terms of the main findings, it is evident that access to private rental housing is not just a matter of ‘supply and demand’. It is also about assessment of risk among applicants. Risk – perceived or actual – is thus a critical factor in deciding who gets housed, and how. Risk and its assessment matter in the context of housing provision and in the development of policy responses. The outcomes from this study also highlight a number of salient points: 1.There are two principal forms of risk associated with property management: financial risk and risk of litigation. 2. Certain tenant characteristics and/or circumstances – ability to pay and ability to care for the rented property – are the main factors focused on in assessing risk among applicants for rental housing. Signals of either ‘(in)ability to pay’ and/or ‘(in)ability to care for the property’ are almost always interpreted as markers of high levels of risk. 3. The processing of tenancy applications entails a complex and variable mix of formal and informal strategies of risk-assessment and allocation where sorting (out), ranking, discriminating and handing over characterise the process. 4. In the eyes of property managers, ‘suitable’ tenants can be conceptualised as those who are resourceful, reputable, competent, strategic and presentable. 5. Property managers clearly articulated concern about risks entailed in a number of characteristics or situations. Being on a low income was the principal and overarching factor which agents considered. Others included: - unemployment - ‘big’ families; sole parent families - domestic violence - marital breakdown - shift from home ownership to private rental - Aboriginality and specific ethnicities - physical incapacity - aspects of ‘presentation’. The financial vulnerability of applicants in these groups can be invoked, alongside expressed concerns about compromised capacities to manage income and/or ‘care for’ the property, as legitimate grounds for rejection or a lower ranking. 6. At the level of face-to-face interaction between the property manager and applicants, more intuitive assessments of risk based upon past experience or ‘gut feelings’ come into play. These judgements are interwoven with more systematic procedures of tenant selection. The findings suggest that considerable ‘risk’ is associated with low-income status, either directly or insofar as it is associated with other forms of perceived risk, and that such risks are likely to impede access to the professionally managed private rental market. Detailed analysis suggests that opportunities for access to housing by low-income householders also arise where, for example: - the ‘local experience’ of an agency and/or property manager works in favour of particular applicants - applicants can demonstrate available social support and financial guarantors - an applicant’s preference or need for longer-term rental is seen to provide a level of financial security for the landlord - applicants are prepared to agree to specific, more stringent conditions for inspection of properties and review of contracts - the particular circumstances and motivations of landlords lead them to consider a wider range of applicants - In particular circumstances, property managers are prepared to give special consideration to applicants who appear worthy, albeit ‘risky’. The strategic actions of demonstrating and documenting on the part of vulnerable (low-income) tenant applicants can improve their chances of being perceived as resourceful, capable and ‘savvy’. Such actions are significant because they help to persuade property managers not only that the applicant may have sufficient resources (personal and material) but that they accept that the onus is on themselves to show they are reputable, and that they have valued ‘competencies’ and understand ‘how the system works’. The parameters of the market do shape the processes of risk-assessment and, ultimately, the strategic relation of power between property manager and the tenant applicant. Low vacancy rates and limited supply of lower-cost rental stock, in all areas, mean that there are many more tenant applicants than available properties, creating a highly competitive environment for applicants. The fundamental problem of supply is an aspect of the market that severely limits the chances of access to appropriate and affordable housing for low-income rental housing applicants. There is recognition of the impact of this problem of supply. The study indicates three main directions for future focus in policy and program development: providing appropriate supports to tenants to access and sustain private rental housing, addressing issues of discrimination and privacy arising in the processes of selecting suitable tenants, and addressing problems of supply.

Microstructural characterization of electron beam evaporated tungsten oxide films for gas sensing applications

Tungsten trioxide is one of the potential semiconducting materials used for sensing NH3, CO, CH4 and acetaldehyde gases. The current research aims at development, microstructural characterization and gas sensing properties of thin films of Tungsten trioxide (WO3). In this paper, we intend to present the microstructural characterization of these films as a function of post annealing heat treatment. Microstructural and elemental analysis of electron beam evaporated WO3 thin films and iron doped WO3 films (WO3:Fe) have been carried out using analytical techniques such as Transmission electron microscopy, Rutherford Backscattered Spectroscopy and XPS analysis. TEM analysis revealed that annealing at 300oC for 1 hour improves cyrstallinity of WO3 film. Both WO3 and WO3:Fe films had uniform thickness and the values corresponded to those measured during deposition. RBS results show a fairly high concentration of oxygen at the film surface as well as in the bulk for both films, which might be due to adsorption of oxygen from atmosphere or lattice oxygen vacancy inherent in WO3 structure. XPS results indicate that tungsten exists in 4d electronic state on the surface but at a depth of 10 nm, both 4d and 4f electronic states were observed. Atomic force microscopy reveals nanosize particles and porous structure of the film. This study shows e-beam evaporation technique produces nanoaparticles and porous WO3 films suitable for gas sensing applications and doping with iron decreases the porosity and particle size which can help improve the gas selectivity.

Characterisation of soils with the use of instrumental techniques : a multivariate forensic study

The value of soil evidence in the forensic discipline is well known. However, it would be advantageous if an in-situ method was available that could record responses from tyre or shoe impressions in ground soil at the crime scene. The development of optical fibres and emerging portable NIR instruments has unveiled a potential methodology which could permit such a proposal. The NIR spectral region contains rich chemical information in the form of overtone and combination bands of the fundamental infrared absorptions and low-energy electronic transitions. This region has in the past, been perceived as being too complex for interpretation and consequently was scarcely utilized. The application of NIR in the forensic discipline is virtually non-existent creating a vacancy for research in this area. NIR spectroscopy has great potential in the forensic discipline as it is simple, nondestructive and capable of rapidly providing information relating to chemical composition. The objective of this study is to investigate the ability of NIR spectroscopy combined with Chemometrics to discriminate between individual soils. A further objective is to apply the NIR process to a simulated forensic scenario where soil transfer occurs. NIR spectra were recorded from twenty-seven soils sampled from the Logan region in South-East Queensland, Australia. A series of three high quartz soils were mixed with three different kaolinites in varying ratios and NIR spectra collected. Spectra were also collected from six soils as the temperature of the soils was ramped from room temperature up to 6000C. Finally, a forensic scenario was simulated where the transferral of ground soil to shoe soles was investigated. Chemometrics methods such as the commonly known Principal Component Analysis (PCA), the less well known fuzzy clustering (FC) and ranking by means of multicriteria decision making (MCDM) methodology were employed to interpret the spectral results. All soils were characterised using Inductively Coupled Plasma Optical Emission Spectroscopy and X-Ray Diffractometry. Results were promising revealing NIR combined with Chemometrics is capable of discriminating between the various soils. Peak assignments were established by comparing the spectra of known minerals with the spectra collected from the soil samples. The temperature dependent NIR analysis confirmed the assignments of the absorptions due to adsorbed and molecular bound water. The relative intensities of the identified NIR absorptions reflected the quantitative XRD and ICP characterisation results. PCA and FC analysis of the raw soils in the initial NIR investigation revealed that the soils were primarily distinguished on the basis of their relative quartz and kaolinte contents, and to a lesser extent on the horizon from which they originated. Furthermore, PCA could distinguish between the three kaolinites used in the study, suggesting that the NIR spectral region was sensitive enough to contain information describing variation within kaolinite itself. The forensic scenario simulation PCA successfully discriminated between the ‘Backyard Soil’ and ‘Melcann® Sand’, as well as the two sampling methods employed. Further PCA exploration revealed that it was possible to distinguish between the various shoes used in the simulation. In addition, it was possible to establish association between specific sampling sites on the shoe with the corresponding site remaining in the impression. The forensic application revealed some limitations of the process relating to moisture content and homogeneity of the soil. These limitations can both be overcome by simple sampling practices and maintaining the original integrity of the soil. The results from the forensic scenario simulation proved that the concept shows great promise in the forensic discipline.

CRE workshop part I : comprehending the context

CRE (Corporate Real Estate) decisions should not simply deal with the management of individual facilities, but should especially be concerned with the relationships that a facility has with the corporate business strategy and with the larger real estate markets. Both the practice and the research of CRE management have historically tended to emphasize real estate issues and ignore the corporation’s business issues, causing real estate strategies to be disconnected from the goal and priorities of the corporation’s senior management. With regard to office cycles, a large number of econometric models have been proposed during the last 20 years. However, evidence from historical data and previous research in the field of real estate forecasting seem to agree only on one thing: the existence of interconnected property cycles that are concentrated on vacancy rates (demand). Vacancy also represents the linkage between the inadequacy of existing CRE strategies and the inability of existing econometric models to correctly forecast office rent cycles. Business cycles, across different industry sectors, have decreased from 5-7 years to 1-3 years today, yet corporations are still entering into leases of 5-10 years, causing hidden vacancy levels to rise. Possibly, once CRE strategies are totally in tune with the overall business, hidden vacancy will fade away providing forecasters with better quality data. The aim of this paper is not to investigate whether and when the supply-side will eventually evolve to provide flexible occupancy arrangements to accommodate corporate agility requirements, but rather to propose a general framework for corporations to improve the decision making process of their CRE executives, while emphasizing the importance of understanding the context as a precondition to effective real estate involvements.

Enhanced photoconduction of free-standing ZnO nanowire films by L-lysine treatment

Flexible paper-like ZnO nanowire films are fabricated and the effect of L-lysine passivation of the nanowire surfaces on improving the UV photoresponse is studied. We prepare three types of nanowires with different defect contents, and find that the L-lysine treatment can suppress the oxygen-vacancy-related photoluminescence as well as enhance the UV photoconduction. The nanowires with fewer defects gain larger enhancement of UV photoconduction after L-lysine treatment. Reproducible UV photoresponse of the devices in humid air is obtained due to L-lysine surface passivation, ruling out the influence of water molecules in degrading the UV photocurrent.

Coupling of energy from quantum emitters to the plasmonic mode of V groove waveguides: A numerical study

This work is a theoretical investigation into the coupling of a single excited quantum emitter to the plasmon mode of a V groove waveguide. The V groove waveguide consists of a triangular channel milled in gold and the emitter is modeled as a dipole emitter, and could represent a quantum dot, nitrogen vacancy in diamond, or similar. In this work the dependence of coupling efficiency of emitter to plasmon mode is determined for various geometrical parameters of the emitter-waveguide system. Using the finite element method, the effect on coupling efficiency of the emitter position and orientation, groove angle, groove depth, and tip radius, is studied in detail. We demonstrate that all parameters, with the exception of groove depth, have a significant impact on the attainable coupling efficiency. Understanding the effect of various geometrical parameters on the coupling between emitters and the plasmonic mode of the waveguide is essential for the design and optimization of quantum dot–V groove devices.

Role of lithium vacancies in accelerating the dehydrogenation kinetics on a LiBH4(010) surface : an Ab initio study

In this work, ab initio density functional calculations were performed to explore the effect of surface lithium vacancies on the initial dehydrogenation kinetics of lithium borohydride. We found that some B−H bonds in neighboring BH4-1 complexes around the vacancy became elongated (weakened). The activation barriers for the recombination of H atoms to form H2 were decreased from 3.64 eV for the stoichiometrically complete LiBH4(010) surface to 1.53 and 0.23 eV in the presence of mono- and di-vacancies, respectively. Our results indicate that the creation of Li vacancies may play a critical role in accelerating the dehydrogenation kinetics of LiBH4.

First-principle studies of the formation and diffusion of hydrogen vacancies in magnesium hydride

Ab initio density functional theory (DFT) calculations are performed to study the formation and diffusion of hydrogen vacancies on MgH2(110) surface and in bulk. We find that the formation energies for a single H-vacancy increase slightly from the surface to deep layers. The energies for creating adjacent surface divancacies at two inplane sites and at an inplane and a bridge site are even smaller than that for the formation of a single H-vacancy, a fact that is attributed to the strong vacancy−vacancy interactions. The diffusion of an H-vacancy from an in-plane site to a bridge site on the surface has the smallest activation barrier calculated at 0.15 eV and should be fast at room temperature. The activation barriers computed for H-vacancy diffusion from the surface into sublayers are all less than 0.70 eV, which is much smaller than the activation energy for desorption of hydrogen on the MgH2(110) surface (1.78−2.80 eV/H2). This suggests that surface desorption is more likely than vacancy diffusion to be rate determining, such that finding effective catalyst on the MgH2 surface to facilitate desorption will be very important for improving overall dehydrogenation performance.

Deformation and failure of graphene sheet and graphene-polymer interface

With a monolayer honeycomb-lattice of sp2-hybridized carbon atoms, graphene has demonstrated exceptional electrical, mechanical and thermal properties. One of its promising applications is to create graphene-polymer nanocomposites with tailored mechanical and physical properties. In general, the mechanical properties of graphene nanofiller as well as graphene-polymer interface govern the overall mechanical performance of graphene-polymer nanocomposites. However, the strengthening and toughening mechanisms in these novel nanocomposites have not been well understood. In this work, the deformation and failure of graphene sheet and graphene-polymer interface were investigated using molecular dynamics (MD) simulations. The effect of structural defects on the mechanical properties of graphene and graphene-polymer interface was investigated as well. The results showed that structural defects in graphene (e.g. Stone-Wales defect and multi-vacancy defect) can significantly deteriorate the fracture strength of graphene but may still make full utilization of corresponding strength of graphene and keep the interfacial strength and the overall mechanical performance of graphene-polymer nanocomposites.

Infrared study of CO adsorption on reduced and oxidised silica-supported copper catalysts

FTIR spectra are reported of CO adsorbed on silica-supported copper catalysts prepared from copper(II) acetate monohydrate. Fully oxidised catalyst gave bands due to CO on CuO, isolated Cu2+ cations on silica and anion vacancy sites in CuO. The highly dispersed CuO aggregated on reduction to metal particles which gave bands due to adsorbed CO characteristic of both low-index exposed planes and stepped sites on high-index planes. Partial surface oxidation with N2O or H2O generated Cu+ adsorption sites which were slowly reduced to Cu° by CO at 300 K. Surface carbonate initially formed from CO was also slowly depleted with time with the generation of CO2. The results are consistent with adsorbed carbonate being an intermediate in the water-gas shift reaction of H2O and CO to H2 and CO2.

Engineering electrodeposited ZnO films and their memristive switching performance

We report the influence of zinc oxide (ZnO) seed layers on the performance of ZnO-based memristive devices fabricated using an electrodeposition approach. The memristive element is based on a sandwich structure using Ag and Pt electrodes. The ZnO seed layer is employed to tune the morphology of the electrodeposited ZnO films in order to increase the grain boundary density as well as construct highly ordered arrangements of grain boundaries. Additionally, the seed layer also assists in optimizing the concentration of oxygen vacancies in the films. The fabricated devices exhibit memristive switching behaviour with symmetrical and asymmetrical hysteresis loops in the absence and presence of ZnO seed layers, respectively. A modest concentration of oxygen vacancy in electrodeposited ZnO films as well as an increase in the ordered arrangement of grain boundaries leads to higher switching ratios in Ag/ZnO/Pt devices.