Shape dependent electrocatalytic behaviour of silver nanoparticles

The electrochemical and electrocatalytic behaviour of silver nanoprisms, nanospheres and nanocubes of comparable size in an alkaline medium have been investigated to ascertain the shape dependent behaviour of silver nanoparticles, which are an extensively studied nanomaterial. The nanomaterials were synthesised using chemical methods and characterised with UV-visible spectroscopy, transmission electron microscopy and X-ray diffraction. The nanomaterials were immobilised on a substrate glassy carbon electrode and characterised by cyclic voltammetry for their surface oxide electrochemistry. The electrocatalytic oxidation of hydrazine and formaldehyde and the reduction of hydrogen peroxide were studied by performing cyclic voltammetric and chronoamperometric experiments for both the nanomaterials and a smooth polycrystalline macrosized silver electrode. In all cases the nanomaterials showed enhanced electrocatalytic activity over the macro-silver electrode. Significantly, the silver nanoprisms that are rich in hcp lamellar defects showed greater activity than nanospheres and nanocubes for all reactions studied.

Electrocrystallization of phase I, CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane), on indium tin oxide and boron-doped diamond electrodes

The electrochemical reduction of TCNQ to TCNQ•- in acetonitrile in the presence of [Cu(MeCN)4]+ has been undertaken at boron-doped diamond (BDD) and indium tin oxide (ITO) electrodes. The nucleation and growth process at BDD is similar to that reported previously at metal electrodes. At an ITO electrode, the electrocrystallization of more strongly adhered, larger, branched, needle-shaped phase I CuTCNQ crystals is detected under potential step conditions and also when the potential is cycled over the potential range of 0.7 to −0.1 V versus Ag/AgCl (3 M KCl). Video imaging can be used at optically transparent ITO electrodes to monitor the growth stage of the very large branched crystals formed during the course of electrochemical experiments. Both in situ video imaging and ex situ X-ray diffraction and scanning electron microscopy (SEM) data are consistent with the nucleation of CuTCNQ taking place at a discrete number of preferred sites on the ITO surface. At BDD electrodes, ex situ optical images show that the preferential growth of CuTCNQ occurs at the more highly conducting boron-rich areas of the electrode, within which there are preferred sites for CuTCNQ formation.

Effect of the mediator in feedback mode-based SECM interrogation of indium tin-oxide and boron-doped diamond electrodes

Indium tin-oxide (ITO) and polycrystalline boron-doped diamond (BDD) have been examined in detail using the scanning electrochemical microscopy technique in feedback mode. For the interrogation of electrodes made from these materials, the choice of mediator has been varied. Using Ru(CN) 4− 6 (aq), ferrocene methanol (FcMeOH), Fe(CN) 3− 6 (aq) and Ru(NH 3) 3+ 6 (aq), approach curve experiments have been performed, and for purposes of comparison, calculations of the apparent heterogeneous electron transfer rates (k app) have been made using these data. In general, it would appear that values of k app are affected mainly by the position of the mediator reversible potential relative to the relevant semiconductor band edge (associated with majority carriers). For both the ITO (n type) and BDD (p type) electrodes, charge transfer is impeded and values are very low when using FcMeOH and Fe(CN) 3− 6 (aq) as mediators, and the use of Ru(NH 3) 3+ 6(aq) results in the largest value of k app. With ITO, the surface is chemically homogeneous and no variation is observed for any given mediator. Data is also presented where the potential of the ITO electrode is fixed using a ratio of the mediators Fe(CN) 3− 6(aq) and Fe(CN) 4− 6(aq). In stark contrast, the BDD electrode is quite the opposite and a range of k app values are observed for all mediators depending on the position on the surface. Both electrode surfaces are very flat and very smooth, and hence, for BDD, variations in feedback current imply a variation in the electrochemical activity. A comparison of the feedback current where the substrate is biased and unbiased shows a surprising degree of proportionality.

Bacterial kinetics-controlled shape-directed biosynthesis of silver nanoplates using Morganella psychrotolerans

We show for the first time that by controlling the growth kinetics of Morganella psychrotolerans, a silver-resistant psychrophilic bacterium, the shape anisotropy of silver nanoparticles can be achieved. This is particularly important considering that there has been no report that demonstrates a control over shape of Ag nanoparticles by controlling the growth kinetics of bacteria during biological synthesis. Additionally, we have for the first time performed electrochemistry experiments on bacterial cells after exposing them to Ag(+) ions, which provide significant new insights about mechanistic aspects of Ag reduction by bacteria. The possibility to achieve nanoparticle shape control by using a "green" biosynthesis approach is expected to open up new exciting avenues for eco-friendly, large-scale, and economically viable shape-controlled synthesis of nanomaterials.

Study of the initial stage of solid electrolyte interphase formation upon chemical reaction of lithium metal and N-Methyl-N-Propyl-Pyrrolidinium-Bis (Fluorosulfonyl) Imide

Chemical reaction studies of N-methyl-N-propyl-pyrrolidinium-bis(fluorosulfonyl)imide-based ionic liquid with the lithium metal surface were performed using ab initio molecular dynamics (aMD) simulations and X-ray Photoelectron Spectroscopy (XPS). The molecular dynamics simulations showed rapid and spontaneous decomposition of the ionic liquid anion, with subsequent formation of long-lived species such as lithium fluoride. The simulations also revealed the cation to retain its structure by generally moving away from the lithium surface. The XPS experiments showed evidence of decomposition of the anion, consistent with the aMD simulations and also of cation decomposition and it is envisaged that this is due to the longer time scale for the XPS experiment compared to the time scale of the aMD simulation. Overall experimental results confirm the majority of species suggested by the simulation. The rapid chemical decomposition of the ionic liquid was shown to form a solid electrolyte interphase composed of the breakdown products of the ionic liquid components in the absence of an applied voltage.

Exploiting the facile oxidation of evaporated gold films to drive electroless silver deposition for the creation of bimetallic Au/Ag surfaces

Gold is often considered as an inert material but it has been unequivocally demonstrated that it possesses unique electronic, optical, catalytic and electrocatalytic properties when in a nanostructured form.[1] For the latter the electrochemical behaviour of gold in aqueous media has been widely studied on a plethora of gold samples, including bulk polycrystalline and single-crystal electrodes, nanoparticles, evaporated films as well as electrodeposited nanostructures, particles and thin films.[1b, 2] It is now well-established that the electrochemical behaviour of gold is not as simple as an extended double-layer charging region followed by a monolayer oxide-formation/-removal process. In fact the so-called double-layer region of gold is significantly more complicated and has been investigated with a variety of electrochemical and surface science techniques. Burke and others[3] have demonstrated that significant processes due to the oxidation of low lattice stabilised atoms or clusters of atoms occur in this region at thermally and electrochemically treated electrodes which were confirmed later by Bond[4] to be Faradaic in nature via large-amplitude Fourier transformed ac voltammetric experiments. Supporting evidence for the oxidation of gold in the double-layer region was provided by Bard,[5] who used a surface interrogation mode of scanning electrochemical microscopy to quantify the extent of this process that forms incipient oxides on the surface. These were estimated to be as high as 20% of a monolayer. This correlated with contact electrode resistance measurements,[6] capacitance measurements[7] and also electroreflection techniques...

Behaviour and design of crest-fixed profiled steel roof claddings under wind uplift

Profiled steel roof claddings in Australia are commonly made of very thin high tensile steel and are crest-fixed with screw fasteners. At present the design of these claddings is entirely based on testing. In order to improve the understanding of the behaviour of these claddings under wind uplift, and thus the design methods, a detailed investigation consisting of a finite element analysis and laboratory experiments was carried out on two-span roofing assemblies of three common roofing profiles. It was found that the failure of the roof cladding system was due to a local failure (dimpling of crests/pull-through) at the fasteners. This paper presents the details of the investigation, the results and then proposes a design method based on the strength of the screwed connections, for which testing of small-scale roofing models and/or using a simple design formula is recommended.

Finite element analysis of hollow flange beams with web stiffeners

A new cold-formed and resistance welded section known as the Hollow Flange Beam (HFB) has been developed recently in Australia. In contrast to the common lateral torsional buckling mode of I-beams, this unique section comprising two stiff triangular flanges and a slender web is susceptible to a lateral distortional buckling mode of failure involving lateral deflection, twist, and cross-section change due to web distortion. This lateral distortional buckling behavior has been shown to cause significant reduction of the available flexural capacity of HFBs. An investigation using finite element analyses and large scale experiments was carried out into the use of transverse web plate stiffeners to improve the lateral buckling capacity of HFBs. This paper presents the details of the finite element model and analytical results. The experimental procedure and results are outlined in a companion paper at this conference.

Finite-element analysis of hollow flange beams with web stiffeners

A new cold-formed and resistance-welded section known as the hollow flange beam (HFB) has been developed recently in Australia. In contrast to the common lateral-torsional buckling mode of I-beams, this unique section comprising two stiff triangular flanges and a slender web is susceptible to a lateral-distortional buckling mode of failure involving lateral deflection, twist, and cross-section change due to web distortion. This lateral-distortional buckling behavior has been shown to cause significant reduction of the available flexural capacity of HFBs. An investigation using finite-element analyses and large-scale experiments was carried out into the use of transverse web plate stiffeners to improve the lateral buckling capacity of HFBs. This paper presents the details of the finite-element model and analytical results. The experimental procedure and results are outlined in a companion paper.

Local plastic mechanisms in thin steel plates under in-plane compression

Thin-walled steel plates subjected to in-plane compression develop two types of local plastic mechanism, namely the roof-shaped mechanism and the so-called flip-disc mechanism, but the intriguing question of why two mechanisms should develop was not answered until recently. It was considered that the location of first yield point shifted from the centre of the plate to the midpoint of the longitudinal edge depending on the b/t ratio, imperfection level, and yield stress of steel, which then decided the type of mechanism. This paper has verified this hypothesis using analysis and laboratory experiments. An elastic analysis using Galerkin's method to solve Marguerre's equations was first used to determine the first yield point, based on which the local plastic mechanism/imperfection tolerance tables have been developed which give the type of mechanism as a function of b/t ratio, imperfection level and yield stress of steel. Laboratory experiments of thin-walled columns verified the imperfection tolerance tables and thus indirectly the hypothesis. Elastic and rigid-plastic curves were them used to predict the effect on the ultimate load due to the change of mechanism. A finite element analysis of selected cases also confirmed the results from simple analyses and experiments.

Local buckling behaviour of steel plate elements supported by a plastic foam material

Sandwich panels comprising steel facings and a polystyrene foam core are increasingly used as roof and wall claddings in buildings in Australia. When they are subjected to loads causing bending and/or axial compression, the steel plate elements of their profiled facing are susceptible to local buckling. However, when compared to panels with no foam core, they demonstrate significantly improved local buckling behaviour because they are supported by foam. In order to quantify such improvements and to validate the use of available design buckling stress formulae, an investigation using finite element analyses and laboratory experiments was carried out on steel plates that are commonly used in Australia of varying yield stress and thickness supported by a polystyrene foam core. This paper presents the details of this investigation, the buckling results and their comparison with available design buckling formulae.

Removal of bisphenol A from wastewater by Ca-montmorillonite modified with selected surfactants

Organo Arizona SAz-2 Ca-montmorillonite was prepared with different surfactant (DDTMA and HDTMA) loadings through direct ion exchange. The structural properties of the prepared organoclays were characterized by XRD and BET instruments. Batch experiments were carried out on the adsorption of bisphenol A (BPA) under different experimental conditions of pH and temperature to determine the optimum adsorption conditions. The hydrophobic phase and positively charged surface created by the loaded surfactant molecules are responsible for the adsorption of BPA. The adsorption of BPA onto organoclays is well described by pseudo-second order kinetic model and the Langmuir isotherm. The maximum adsorption capacity of the organoclays for BPA obtained from a Langmuir isotherm was 151.52 mg/g at 297 K. This value is among the highest values for BPA adsorption compared with other adsorbents. In addition, the adsorption process was spontaneous and exothermic based on the adsorption thermodynamics study. The organoclays intercalated with longer chain surfactant molecules possessed a greater adsorption capacity for BPA even under alkaline conditions. This process provides a pathway for the removal of BPA from contaminated waters.

Shear capacity of lipped channel beams with web openings : design rules and improvements

Cold-formed steel Lipped Channel Beams (LCB) with web openings are commonly used as floor joists and bearers in building structures. Shear behaviour of these beams is more complicated and their shear capacities are considerably reduced by the presence of web openings. Hence detailed numerical and experimental studies of simply supported LCBs under a mid-span load with aspect ratios of 1.0 and 1.5 were undertaken to investigate the shear behaviour and strength of LCBs with web openings. Experimental and numerical results showed that the current design rules in cold-formed steel structures design codes are very conservative. Improved design equations were therefore proposed for the shear strength of LCBs with web openings based on both experimental and numerical results. This research showed a significant reduction in shear capacities of LCBs when large web openings are included for the purpose of locating building services. A cost effective method of eliminating such detrimental effects of large circular web openings was also therefore investigated using experimental and numerical studies. For this purpose LCBS were reinforced using plate, stud, transverse and sleeve stiffeners with varying sizes and thicknesses that were welded and screw-fastened to the web of LCBs. These studies showed that plate stiffeners were the most suitable. Suitable screw-fastened plate stiffener arrangements with optimum thicknesses were then proposed for LCBs with web openings to restore their original shear capacities. This paper presents the details of finite element analyses and experiments of LCBs with web openings in shear, and the development of improved shear design rules. It then describes the experimental and numerical studies to determine the optimum plate stiffener arrangements and the results. The proposed shear design rules in this paper can be considered for inclusion in the future versions of cold-formed steel design codes.

XML clustering and its application to XML transformation

The continuous growth of the XML data poses a great concern in the area of XML data management. The need for processing large amounts of XML data brings complications to many applications, such as information retrieval, data integration and many others. One way of simplifying this problem is to break the massive amount of data into smaller groups by application of clustering techniques. However, XML clustering is an intricate task that may involve the processing of both the structure and the content of XML data in order to identify similar XML data. This research presents four clustering methods, two methods utilizing the structure of XML documents and the other two utilizing both the structure and the content. The two structural clustering methods have different data models. One is based on a path model and other is based on a tree model. These methods employ rigid similarity measures which aim to identifying corresponding elements between documents with different or similar underlying structure. The two clustering methods that utilize both the structural and content information vary in terms of how the structure and content similarity are combined. One clustering method calculates the document similarity by using a linear weighting combination strategy of structure and content similarities. The content similarity in this clustering method is based on a semantic kernel. The other method calculates the distance between documents by a non-linear combination of the structure and content of XML documents using a semantic kernel. Empirical analysis shows that the structure-only clustering method based on the tree model is more scalable than the structure-only clustering method based on the path model as the tree similarity measure for the tree model does not need to visit the parents of an element many times. Experimental results also show that the clustering methods perform better with the inclusion of the content information on most test document collections. To further the research, the structural clustering method based on tree model is extended and employed in XML transformation. The results from the experiments show that the proposed transformation process is faster than the traditional transformation system that translates and converts the source XML documents sequentially. Also, the schema matching process of XML transformation produces a better matching result in a shorter time.

Group interactions in science practical work

This study explored the interactions of a highly motivated group of students doing traditional practical work in science. Interest focussed on the social construction of understanding and how this could be described. Despite considerable collaboration in constructing an understanding of the task the students rarely focussed on the concepts the practical work was intended to illustrate. Collaboration was described in terms of social behaviours and discourse moves which supported the use of cognitive strategies.