The role of Ti as a catalyst for the dissociation of hydrogen on a Mg(0001) surface

In this paper, the dissociative chemisorption of hydrogen on both pure and Ti-incorporated Mg(0001) surfaces are studied by ab initio density functional theory (DFT) calculations. The calculated dissociation barrier of hydrogen molecule on a pure Mg(0001) surface (1.05 eV) is in good agreement with comparable theoretical studies. For the Ti-incorporated Mg(0001) surface, the activated barrier decreases to 0.103 eV due to the strong interaction between the molecular orbital of hydrogen and the d metal state of Ti. This could explain the experimentally observed improvement in absorption kinetics of hydrogen when transition metals have been introduced into the magnesium materials.

Educating the ‘Design Innovation Catalyst’ for change

Conventionally, design has played a compartmental role in the innovation process within most conservative companies around the world. Generally, companies have focused on the product design execution or the manufacturing and production arenas, and in some instances design is seen as merely a stylistic afterthought. Gradually, design is being regarded as a dynamic and central tactical business resource and consequently organisations globally look to design to help them innovate, differentiate and compete in a changing economic climate. Considering this, the question is raised; how can the specific knowledge and skills of designers be better articulated, understood, implemented and valued as a core component of strategic innovation in businesses? In seeking to answer this question, this paper proposes the new frontier of the design profession coined the ‘Design Innovation Catalyst’. This paper outlines the role of the new design professional and discusses the subsequent implications for design education. Furthermore, questions surrounding how designers will develop these new capabilities and how the design led innovation framework in application can contribute to the future of design will also be presented. It is anticipated that the findings from this research will help to better equip designers to enable them to play a more central role in business and strategic innovation now and in the future.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

SERS based detection of barcoded gold nanoparticle assemblies from within animal tissue

We have explored the potential of deep Raman spectroscopy, specifically surface enhanced spatially offset Raman spectroscopy (SESORS), for non-invasive detection from within animal tissue, by employing SERS-barcoded nanoparticle (NP) assemblies as the diagnostic agent. This concept has been experimentally verified in a clinic-relevant backscattered Raman system with an excitation line of 785 nm under ex vivo conditions. We have shown that our SORS system, with a fixed offset of 2-3 mm, offered sensitive probing of injected QTH-barcoded NP assemblies through animal tissue containing both protein and lipid. In comparison to that of non-aggregated SERS-barcoded gold NPs, we have demonstrated that the tailored SERS-barcoded aggregated NP assemblies have significantly higher detection sensitivity. We report that these NP assemblies can be readily detected at depths of 7-8 mm from within animal proteinaceous tissue with high signal-to-noise (S/N) ratio. In addition they could also be detected from beneath 1-2 mm of animal tissue with high lipid content, which generally poses a challenge due to high absorption of lipids in the near-infrared region. We have also shown that the signal intensity and S/N ratio at a particular depth is a function of the SERS tag concentration used and that our SORS system has a QTH detection limit of 10-6 M. Higher detection depths may possibly be obtained with optimization of the NP assemblies, along with improvements in the instrumentation. Such NP assemblies offer prospects for in vivo, non-invasive detection of tumours along with scope for incorporation of drugs and their targeted and controlled release at tumour sites. These diagnostic agents combined with drug delivery systems could serve as a “theranostic agent”, an integration of diagnostics and therapeutics into a single platform.

School libraries, teacher-librarians and literacy at Gold Coast schools : research findings

This paper reports research about school libraries, teacher-librarians and their contribution to literacy development. It presents an evidenced based snapshot, from the principals’ perspective, of 27 school libraries in the Gold Coast area of Australia. These new Australian findings show: • an evidenced based snapshot of school libraries and teacher-librarians, from the principals’ perspective • indications that school NAPLAN scores for reading and writing were generally higher when (a) student to library staff ratios were lower (i.e. better) and (b) the school had a teacher-librarian. The research responds to the Australian Government inquiry into school libraries and teacher-librarians (2010-11) which identified an urgent need for current data about provision and staffing of school libraries and their influence on student literacy and learning. In light of the National plan for school improvement (Australian Government, 2013), the findings are of potential interest to education authorities, school leadership teams, teacher-librarians, teachers and researchers. They offer evidence to inform policy development, strategic planning and advocacy about school libraries and teacher-librarians in supporting the reading, literacy and learning needs of 21st century learners.

Optimal catalyst thickness in titanium dioxide fixed film reactors: Mathematical modelling and experimental validation

The use of immobilised TiO2 for the purification of polluted water streams introduces the necessity to evaluate the effect of mechanisms such as the transport of pollutants from the bulk of the liquid to the catalyst surface and the transport phenomena inside the porous film. Experimental results of the effects of film thickness on the observed reaction rate for both liquid-side and support-side illumination are here compared with the predictions of a one-dimensional mathematical model of the porous photocatalytic slab. Good agreement was observed between the experimentally obtained photodegradation of phenol and its by-products, and the corresponding model predictions. The results have confirmed that an optimal catalyst thickness exists and, for the films employed here, is 5 μm. Furthermore, the modelling results have highlighted the fact that porosity, together with the intrinsic reaction kinetics are the parameters controlling the photocatalytic activity of the film. The former by influencing transport phenomena and light absorption characteristics, the latter by naturally dictating the rate of reaction.

Supported gold nanoparticles as photocatalysts utilising the full solar spectrum for organic synthesis

This thesis is an innovative study for organic synthesis using supported gold nanoparticles as photocatalysts under visible light irradiation. It especially examines a novel green process for efficient hydroamination of alkynes with amines. The investigation of other traditional reduction and oxidation reactions also adds significantly to the knowledge of gold nanoparticles and titania nanofibres as photocatalysts for organic synthesis.

Improved catalyst, particularly for emission control

A catalyst comprising a catalytic material supported on a support, characterized in that the support comprises particles predominantly having a max. particle size of less than 1000 nm and an aspect ratio of greater than, and the. catalytic material is mainly present in the form of discrete islands of catalytic material supported on the support, with a substantial proportion of the islands of catalytic material being sep. and isolated from other islands of catalytic material. The islands of catalytic material are sep. and isolated from other islands of catalytic material such that diffusion and growth of the islands of catalytic material at elevated temp. is minimized or avoided. The disclosure and examples pertain to emission control catalysts. [on SciFinder(R)]

Generation of active surface states of gold and the role of such states in electrocatalysis

The cyclic voltammetry behaviour of gold in aqueous media is often regarded in very simple terms as a combination of two distinct processes, double layer charging/discharging and monolayer oxide formation/removal. This view is questioned here on the basis of both the present results and earlier independent data by other authors. It was demonstrated in the present case that both severe cathodization or thermal pretreatment of polycrystalline gold in acid solution resulted in the appearance of substantial Faradaic responses in the double layer region. Such anamolous behaviour, as outlined recently also for other metals, is rationalized in terms of the presence of active metal atoms (which undergo premonolayer oxidation) at the electrode surface. Such behaviour, which is also assumed to correspond to that of active sites on conventional gold surfaces, is assumed to be of vital importance in electrocatalysis; in many instances the latter process is also quite marked in the double layer region.

Premonolayer oxidation of nanostructured gold : an important factor influencing electrocatalytic activity

The study of the electrodeposition of polycrystalline gold in aqueous solution is important from the viewpoint that in electrocatalysis applications ill-defined micro- and nanostructured surfaces are often employed. In this work, the morphology of gold was controlled by the electrodeposition potential and the introduction of Pb(CH3COO)2•3H2O into the plating solution to give either smooth or nanostructured gold crystallites or large dendritic structures which have been characterized by scanning electron microscopy (SEM). The latter structures were achieved through a novel in situ galvanic replacement of lead with AuCl4−(aq) during the course of gold electrodeposition. The electrochemical behavior of electrodeposited gold in the double layer region was studied in acidic and alkaline media and related to electrocatalytic performance for the oxidation of hydrogen peroxide and methanol. It was found that electrodeposited gold is a significantly better electrocatalyst than a polished gold electrode; however, performance is highly dependent on the chosen deposition parameters. The fabrication of a deposit with highly active surface states, comparable to those achieved at severely disrupted metal surfaces through thermal and electrochemical methods, does not result in the most effective electrocatalyst. This is due to significant premonolayer oxidation that occurs in the double layer region of the electrodeposited gold. In particular, in alkaline solution, where gold usually shows the most electrocatalytic activity, these active surface states may be overoxidized and inhibit the electrocatalytic reaction. However, the activity and morphology of an electrodeposited film can be tailored whereby electrodeposited gold that exhibits nanostructure within the crystallites on the surface demonstrated enhanced electrocatalytic activity compared to smaller smooth gold crystallites and larger dendritic structures in potential regions well within the double layer region.

Study of the underlying electrochemistry of polycrystalline gold electrodes in aqueous solution and electrocatalysis by large amplitude Fourier transformed alternating current voltammetry

Polycrystalline gold electrodes of the kind that are routinely used in analysis and catalysis in aqueous media are often regarded as exhibiting relatively simple double-layer charging/discharging and monolayer oxide formation/ removal in the positive potential region. Application of the large amplitude Fourier transformed alternating current (FT-ac) voltammetric technique that allows the faradaic current contribution of fast electron-transfer processes to be emphasized in the higher harmonic components has revealed the presence of well-defined faradaic (premonolayer oxidation) processes at positive potentials in the double-layer region in acidic and basic media which are enhanced by electrochemical activation. These underlying quasi-reversible interfacial electron-transfer processes may mediate the course of electrocatalytic oxidation reactions of hydrazine, ethylene glycol, and glucose on gold electrodes in aqueous media. The observed responses support key assumptions associated with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis.

High energy states of gold and their importance in electrocatalytic processes at surfaces and interfaces

The ability of metals to store or trap considerable amounts of energy, and thus exist in a non-equilibrium or metastable state, is very well known in metallurgy; however, such behaviour, which is intimately connected with the defect character of metals, has been largely ignored in noble metal surface electrochemistry. Techniques for generating unusually high energy surface states for gold, and the unusual voltammetric responses of such states, are outlined. The surprisingly high (and complex) electrocatalytic activity of gold in aqueous media is attributed to the presence of a range of such non-equilibrium states as the vital entities at active sites on conventional gold surfaces. The possible relevance of these ideas to account for the remarkable catalytic activity of oxide-supported gold microparticles is briefly outlined.

Auto-inhibition of hydrogen gas evolution on gold in aqueous acid solution

It was demonstrated recently that dramatic changes in the redox behaviour of gold/aqueous solution interfaces may be observed following either cathodic or thermal electrode pretreatment. Further work on the cathodic pretreatment of gold in acid solution revealed that as the activity of the gold surface was increased, its performance as a substrate for hydrogen gas evolution under constant potential conditions deteriorated. The change in activity of the gold atoms at the interface, which was attributed to a hydrogen embrittlement process (the occurrence of the latter was subsequently checked by surface microscopy), was confirmed, as in earlier work, by the appearance of a substantial anodic peak at ca. 0.5 V (RHE) in a post-activation positive sweep. Changes in the catalytic activity of a metal surface reflect the fact that the structure (or topography), thermodynamic activity and electronic properties of a surface are dependent not only on pretreatment but also, in the case of the hydrogen evolution reaction, vary with time during the course of reaction. As will be reported shortly, similar (and often more dramatic) time-dependent behaviour was observed for hydrogen gas evolution on other metal electrodes.

Gold nanospikes formed through a simple electrochemical route with high electrocatalytic and surface enhanced Raman scattering activity

We demonstrate a simple electrochemical route to produce uniformly sized gold nanospikes without the need for a capping agent or prior modification of the electrode surface, which are predominantly oriented in the {111} crystal plane and exhibit promising electrocatalytic and SERS properties.