Anaerobic oxidation of ethanol over spinel mixed oxides: the first step in the steam-iron process for H2 production

The future hydrogen demand is expected to increase, both in existing industries (including upgrading of fossil fuels or ammonia production) and in new technologies, like fuel cells. Nowadays, hydrogen is obtained predominantly by steam reforming of methane, but it is well known that hydrocarbon based routes result in environmental problems and besides the market is dependent on the availability of this finite resource which is suffering of rapid depletion. Therefore, alternative processes using renewable sources like wind, solar energy and biomass, are now being considered for the production of hydrogen. One of those alternative methods is the so-called “steam-iron process” which consists in the reduction of a metal-oxide by hydrogen-containing feedstock, like ethanol for instance, and then the reduced material is reoxidized with water to produce “clean” hydrogen (water splitting). This kind of thermochemical cycles have been studied before but currently some important facts like the development of more active catalysts, the flexibility of the feedstock (including renewable bio-alcohols) and the fact that the purification of hydrogen could be avoided, have significantly increased the interest for this research topic. With the aim of increasing the understanding of the reactions that govern the steam-iron route to produce hydrogen, it is necessary to go into the molecular level. Spectroscopic methods are an important tool to extract information that could help in the development of more efficient materials and processes. In this research, ethanol was chosen as a reducing fuel and the main goal was to study its interaction with different catalysts having similar structure (spinels), to make a correlation with the composition and the mechanism of the anaerobic oxidation of the ethanol which is the first step of the steam-iron cycle. To accomplish this, diffuse reflectance spectroscopy (DRIFTS) was used to study the surface composition of the catalysts during the adsorption of ethanol and its transformation during the temperature program. Furthermore, mass spectrometry was used to monitor the desorbed products. The set of studied materials include Cu, Co and Ni ferrites which were also characterized by means of X-ray diffraction, surface area measurements, Raman spectroscopy, and temperature programmed reduction.

New dimeric supramolecular structure of mixed (phthalocyaninato)(porphyrinato)-europium(III) sandwiches : preparation and spectroscopic characteristics

The mixed double-decker Eu\[Pc(15C5)4](TPP) (1) was obtained by base-catalysed tetramerisation of 4,5-dicyanobenzo-15-crown-5 using the half-sandwich complex Eu(TPP)(acac) (acac = acetylacetonate), generated in situ, as the template. For comparative studies, the mixed triple-decker complexes Eu2\[Pc(15C5)4](TPP)2 (2) and Eu2\[Pc(15C5)4]2(TPP) (3) were also synthesised by the raise-by-one-story method. These mixed ring sandwich complexes were characterised by various spectroscopic methods. Up to four one-electron oxidations and two one-electron reductions were revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). As shown by electronic absorption and infrared spectroscopy, supramolecular dimers (SM1 and SM3) were formed from the corresponding double-decker 1 and triple-decker 3 in the presence of potassium ions in MeOH/CHCl3.

Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.

Raman spectroscopic study of the mixed anion mineral Yecoraite Bi5Fe3O9(Te4+O3)(Te6+O4)2•9H2O

Tellurates are rare minerals as the tellurate anion is readily reduced to the tellurite ion. Often minerals with both tellurate and tellurite anions in the mineral are found. An example of such a mineral containing tellurate and tellurite is yecoraite. Raman spectroscopy has been used to study this mineral, the exact structure of which is unknown. Two Raman bands at 796 and 808 cm-1 are assigned to the ν1 (TeO4)2- symmetric and ν3 (TeO3)2- antisymmetric stretching modes and Raman bands at 699 cm-1 are attributed to the the ν3 (TeO4)2- antisymmetric stretching mode and the band at 690 cm-1 to the ν1 (TeO3)2- symmetric stretching mode. The intense band at 465 cm-1 with a shoulder at 470 cm-1 is assigned the (TeO4)2- and (TeO3)2- bending modes. Prominent Raman bands are observed at 2878, 2936, 3180 and 3400 cm-1. The band at 3936 cm-1 appears quite distinct and the observation of multiple bands indicates the water molecules in the yecoraite structure are not equivalent. The values for the OH stretching vibrations listed provide hydrogen bond distances of 2.625 Å (2878 cm-1), 2.636 Å (2936 cm-1), 2.697 Å (3180 cm-1) and 2.798 Å (3400 cm-1). This range of hydrogen bonding contributes to the stability of the mineral. A comparison of the Raman spectra of yecoraite with that of tellurate containing minerals kuranakhite, tlapallite and xocomecatlite is made.

Kava Anxiety Depression Spectrum Study (KADSS): a mixed methods RCT using an aqueous extract of Piper methysticum

Objectives: To report on the design, significance and potential impacts of the first documented human clinical trial assessing the anxiolytic and thymoleptic efficacy of an aqueous monoextract of Piper methysticum (kava). The significance of the qualitative element of our clinical trial is also explored. The Kava Anxiety Depression Spectrum Study (KADSS) is a 3-week placebocontrolled, double-blind, cross-over trial involving 60 adult participants (18—65) with elevated stable anxiety and varying levels of depressive symptoms. Aims: The aims of KADSS are: (1) to determine whether an aqueous standardised extract of kava is effective for the treatment of anxiety; (2) to assess the effects of kava on differing levels of depression; and (3) to explore participants’ experience of taking kava via qualitative research. The study also provides preliminary assessment of the safety of an aqueous extract of kava in humans. Conclusion: If results reveal that the aqueous kava preparation exerts significant anxiolytic effects and appears safe, potentially beneficial impacts may occur. Data supporting a safe and effective kava extract may encourage a re-introduction of kava to Europe, UK and Canada. This may provide a major socioeconomic benefit to Pacific Island nations, and to sufferers of anxiety disorders.

Raman spectroscopic study of the mixed anion sulphate-arsenate mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O has been studied by Raman spectroscopy. Characteristic bands associated with arsenate, sulphate, hydroxyl units are identified. Broad bands are observed and are resolved into component bands. Two intense bands at 859 and 830 cm-1 are assigned to the 1 (AsO4)3- symmetric stretching and 3 (AsO4)3- antisymmetric stretching modes. The comparatively sharp band at 976 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode and a broad spectral profile centered upon 1097 cm-1 is attributed to the ν3 (SO4)2- antisymmetric stretching mode. A comparison of the Raman spectra is made with other arsenate bearing minerals such as carminite, clinotyrolite, kankite, tilasite and pharmacosiderite.

The role of rural land in mixed asset investment portfolios

Rural land has not always been considered as a major long-term investment with both institutional investors and absentee owners in countries such as U.K. and Australia. Although rural land is included in both single asset and mixed asset portfolios in the U.S, it is not at the same levels as either commercial or industrial property. Rural land occupies over 50% of the total area of Australia, and comprises over 115,000 economic farm properties (excludes rural residential, hobby farms and rural lifestyle blocks. However, less than 1.6% of the total economic farm numbers are actually owned by corporate or institutional investors. This low level of corporate involvement in the Australian rural property market has limited both the investment performance research and inclusion of this rural land type in both property and mixed asset investment portfolios. In the U.S. rural land is also the most extensive real estate type based on total area occupied. The United States Department of Agriculture statistics (1998) show that in 1997 there were 2.06 million farms in the U.S., covering 968 million acres, with a total value of $912 billion and generating an annual income of $202 billion. The level of corporate ownership of farms in the U.S. is also higher than the level of corporate farm ownership in Australia. This high level of institutional ownership in rural land in U.S has provided the opportunity for the rural property asset class to be analysed in relation to it’s investment performance and possible role in a mixed asset or mixed property investment portfolio.

An experiment in mixed compilation/interpretation

One of the classic forms of intermediate representation used for communication between compiler front-ends and back-ends are those based on abstract stack machines. It is possible to compile the stack machine instructions into machine code by means of an interpretive code generator, or to simulate the stack machine at runtime using an interpreter. This paper describes an approach intermediate between these two extremes. The front-end for a commercial Modula 2 compiler was ported to the "industry standard PC", and a partially compiling back-end written. The object code runs with the assistance of an interpreter, but may be linked with libraries which are fully compiled. The intent was to provide a programming environment on the PC which is identical to that of the same compilers on 32-bit UNIX machines. This objective has been met, and the compiler is available to educational institutions as free-ware. The design basis of the new compiler is described, and the performance critically evaluated.

Vitamin D and sun protection : the impact of mixed public health messages in Australia

Exposure of the skin to sunlight can cause skin cancer and is also necessary for cutaneous vitamin D production. Media reports have highlighted the purported health benefits of vitamin D. Our aim was to examine attitudes and behaviours related to sun protection and vitamin D. A cross-sectional study of 2,001 residents in Queensland, Australia aged 20-70 years was undertaken. Information collected included: skin cancer risk factors; perceptions about levels of sun exposure required to maintain vitamin D; belief that sun protection increases risk of vitamin D deficiency; intention, and actual change in sun protection practices for adults and children. Multivariate models examined predictors of attitudinal and behavioural change. One-third (32%) believed a fair-skinned adult, and 31% thought a child required at least 30 minutes per day in summer sun to maintain vitamin D levels. Reductions in sun protection were reported by 21% of adults and 14% of children. Factors associated with belief that sun protection may result in not obtaining enough vitamin D included aged ≥ 60 years (OR=1.35, 95% CI 1.09-1.66) and having skin that tanned easily (OR=1.96, 95% CI 1.38-2.78). Participants from low income households, and those who frequently used sun protective clothing were more likely to have reduced sun protection practices (OR=1.33, 95% CI 1.10-1.73 and OR=1.73, 95% CI 1.36-2.20, respectively). This study provides evidence of reductions in sun protection practices in a population living in a high UV environment. There is an urgent need to re-focus messages regarding sun exposure and for continued sun protection practices.

Digital kids, analogue students : a mixed methods study of students' engagement with a school-based Web 2.0 learning innovation

The inquiry documented in this thesis is located at the nexus of technological innovation and traditional schooling. As we enter the second decade of a new century, few would argue against the increasingly urgent need to integrate digital literacies with traditional academic knowledge. Yet, despite substantial investments from governments and businesses, the adoption and diffusion of contemporary digital tools in formal schooling remain sluggish. To date, research on technology adoption in schools tends to take a deficit perspective of schools and teachers, with the lack of resources and teacher ‘technophobia’ most commonly cited as barriers to digital uptake. Corresponding interventions that focus on increasing funding and upskilling teachers, however, have made little difference to adoption trends in the last decade. Empirical evidence that explicates the cultural and pedagogical complexities of innovation diffusion within long-established conventions of mainstream schooling, particularly from the standpoint of students, is wanting. To address this knowledge gap, this thesis inquires into how students evaluate and account for the constraints and affordances of contemporary digital tools when they engage with them as part of their conventional schooling. It documents the attempted integration of a student-led Web 2.0 learning initiative, known as the Student Media Centre (SMC), into the schooling practices of a long-established, high-performing independent senior boys’ school in urban Australia. The study employed an ‘explanatory’ two-phase research design (Creswell, 2003) that combined complementary quantitative and qualitative methods to achieve both breadth of measurement and richness of characterisation. In the initial quantitative phase, a self-reported questionnaire was administered to the senior school student population to determine adoption trends and predictors of SMC usage (N=481). Measurement constructs included individual learning dispositions (learning and performance goals, cognitive playfulness and personal innovativeness), as well as social and technological variables (peer support, perceived usefulness and ease of use). Incremental predictive models of SMC usage were conducted using Classification and Regression Tree (CART) modelling: (i) individual-level predictors, (ii) individual and social predictors, and (iii) individual, social and technological predictors. Peer support emerged as the best predictor of SMC usage. Other salient predictors include perceived ease of use and usefulness, cognitive playfulness and learning goals. On the whole, an overwhelming proportion of students reported low usage levels, low perceived usefulness and a lack of peer support for engaging with the digital learning initiative. The small minority of frequent users reported having high levels of peer support and robust learning goal orientations, rather than being predominantly driven by performance goals. These findings indicate that tensions around social validation, digital learning and academic performance pressures influence students’ engagement with the Web 2.0 learning initiative. The qualitative phase that followed provided insights into these tensions by shifting the analytics from individual attitudes and behaviours to shared social and cultural reasoning practices that explain students’ engagement with the innovation. Six indepth focus groups, comprising 60 students with different levels of SMC usage, were conducted, audio-recorded and transcribed. Textual data were analysed using Membership Categorisation Analysis. Students’ accounts converged around a key proposition. The Web 2.0 learning initiative was useful-in-principle but useless-in-practice. While students endorsed the usefulness of the SMC for enhancing multimodal engagement, extending peer-topeer networks and acquiring real-world skills, they also called attention to a number of constraints that obfuscated the realisation of these design affordances in practice. These constraints were cast in terms of three binary formulations of social and cultural imperatives at play within the school: (i) ‘cool/uncool’, (ii) ‘dominant staff/compliant student’, and (iii) ‘digital learning/academic performance’. The first formulation foregrounds the social stigma of the SMC among peers and its resultant lack of positive network benefits. The second relates to students’ perception of the school culture as authoritarian and punitive with adverse effects on the very student agency required to drive the innovation. The third points to academic performance pressures in a crowded curriculum with tight timelines. Taken together, findings from both phases of the study provide the following key insights. First, students endorsed the learning affordances of contemporary digital tools such as the SMC for enhancing their current schooling practices. For the majority of students, however, these learning affordances were overshadowed by the performative demands of schooling, both social and academic. The student participants saw engagement with the SMC in-school as distinct from, even oppositional to, the conventional social and academic performance indicators of schooling, namely (i) being ‘cool’ (or at least ‘not uncool’), (ii) sufficiently ‘compliant’, and (iii) achieving good academic grades. Their reasoned response therefore, was simply to resist engagement with the digital learning innovation. Second, a small minority of students seemed dispositionally inclined to negotiate the learning affordances and performance constraints of digital learning and traditional schooling more effectively than others. These students were able to engage more frequently and meaningfully with the SMC in school. Their ability to adapt and traverse seemingly incommensurate social and institutional identities and norms is theorised as cultural agility – a dispositional construct that comprises personal innovativeness, cognitive playfulness and learning goals orientation. The logic then is ‘both and’ rather than ‘either or’ for these individuals with a capacity to accommodate both learning and performance in school, whether in terms of digital engagement and academic excellence, or successful brokerage across multiple social identities and institutional affiliations within the school. In sum, this study takes us beyond the familiar terrain of deficit discourses that tend to blame institutional conservatism, lack of resourcing and teacher resistance for low uptake of digital technologies in schools. It does so by providing an empirical base for the development of a ‘third way’ of theorising technological and pedagogical innovation in schools, one which is more informed by students as critical stakeholders and thus more relevant to the lived culture within the school, and its complex relationship to students’ lives outside of school. It is in this relationship that we find an explanation for how these individuals can, at the one time, be digital kids and analogue students.