16 research outputs found
Why do people file share unlawfully? A systematic review, meta-analysis and panel study
Unlawful digital media sharing is common and believed to be extremely damaging to business. Understanding unlawful file sharers’ motivations offers the opportunity to develop business models and behavioral interventions to maximize consumers’ and businesses’ benefit. This paper uses a systematic review of unlawful file sharing research, and the Theory of Planned Behavior, to motivate a large-scale panel study in which initial determinants were used to predict subsequent behavior. A meta-analysis found Attitudes, Subjective Norms and Perceived Behavioral Control were all associated with unlawful file sharing. Media type and demographic differences in the importance of Perceived Behavioral Control were found and attributed to more accurate evaluation of familiar activities, i.e., greater experience increases the influence of Perceived Behavioral Control but age does not. The panel study confirmed that greater past experience was associated with Perceived Behavioral Control and Intention. We conclude that past experience increases the efficacy of the Theory of Planned Behavior and specifically Perceived Behavioral control in predicting behavior, contrary to some widely held beliefs about the role of experience. The role of experience is therefore crucial to understanding people’s choices. Practically, improving social approval, positive evaluation and access to lawful media should reduce unlawful behavior
The active site behaviour of electrochemically synthesised gold nanomaterials
Even though gold is the noblest of metals, a weak chemisorber and is regarded as being quite inert, it demonstrates significant electrocatalytic activity in its nanostructured form. It is demonstrated here that nanostructured and even evaporated thin films of gold are covered with active sites which are responsible for such activity. The identification of these sites is demonstrated with conventional electrochemical techniques such as cyclic voltammetry as well as a large amplitude Fourier transformed alternating current (FT-ac) method under acidic and alkaline conditions. The latter technique is beneficial in determining if an electrode process is either Faradaic or capacitive in nature. The observed behaviour is analogous to that observed for activated gold electrodes whose surfaces have been severely disrupted by cathodic polarisation in the hydrogen evolution region. It is shown that significant electrochemical oxidation responses occur at discrete potential values well below that for the formation of the compact monolayer oxide of bulk gold and are attributed to the facile oxidation of surface active sites. Several electrocatalytic reactions are explored in which the onset potential is determined by the presence of such sites on the surface. Significantly, the facile oxidation of active sites is used to drive the electroless deposition of metals such as platinum, palladium and silver from their aqueous salts on the surface of gold nanostructures. The resultant surface decoration of gold with secondary metal nanoparticles not only indicates regions on the surface which are rich in active sites but also provides a method to form interesting bimetallic surfaces
Decoration of active sites to create bimetallic surfaces and its implication for electrochemical processes
The creation of electrocatalysts based on noble metals has received a significant amount of research interest due to their extensive use as fuel cell catalysts and electrochemical sensors. There have been many attempts to improve the activity of these metals through creating nanostructures, as well as post-synthesis treatments based on chemical, electrochemical, sonochemical and thermal approaches. In many instances these methods result in a material with active surface states, which can be considered to be adatoms or clusters of atoms on the surface that have a low lattice co-ordination number making them more prone to electrochemical oxidation at a wide range of potentials that are significantly less positive than those of their bulk metal counterparts. This phenomenon has been termed pre-monolayer oxidation and has been reported to occur on a range of metallic surfaces. In this work we present findings on the presence of active sites on Pd that has been: evaporated as a thin film; electrodeposited as nanostructures; as well as commercially available Pd nanoparticles supported on carbon. Significantly, advantage is taken of the low oxidation potential of these active sites whereby bimetallic surfaces are created by the spontaneous deposition of Ag from AgNO3 to generate Pd/Ag surfaces. Interestingly this approach does not increase the surface area of the original metal but has significant implications for its further use as an electrode material. It results in the inhibition or promotion of electrocatalytic activity which is highly dependent on the reaction of interest. As a general approach the decoration of active catalytic materials with less active metals for a particular reaction also opens up the possibility of investigating the role of the initially present active sites on the surface and identifying the degree to which they are responsible for electrocatalytic activity
Honeycomb nanogold networks with highly active sites
The formation of macroporous honeycomb gold using an electrochemically generated hydrogen bubble template is described. The synthesis procedure induces the formation of highly active surfaces with enhanced electrocatalytic and surface enhanced Raman scattering properties
Electrochemical formation of platinum nanostructures for fuel cell applications
We report the electrodeposition of platinum on evaporated gold substrates, which provides a method of synthesising surfaces which are active towards the oxidation of methanol. The inclusion of an inorganic growth direction agent is seen to provide a means of altering both the morphology of the deposits as well as their electrocatalytic behaviour.</p
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
Probing the effect of charge transfer enhancement in off resonance mode SERS via conjugation of the probe dye between silver nanoparticles and metal substrates
The charge transfer-mediated surface enhanced Raman scattering (SERS) of crystal violet (CV) molecules that were chemically conjugated between partially polarized silver nanoparticles and optically smooth gold and silver substrates has been studied under off-resonant conditions. Tyrosine molecules were used as a reducing agent to convert silver ions into silver nanoparticles where oxidised tyrosine caps the silver nanoparticle surface with its semiquinone group. This binding through the quinone group facilitates charge transfer and results in partially oxidised silver. This establishes a chemical link between the silver nanoparticles and the CV molecules, where the positively charged central carbon of CV molecules can bind to the terminal carboxylate anion of the oxidised tyrosine molecules. After drop casting Ag nanoparticles bound with CV molecules it was found that the free terminal amine groups tend to bind with the underlying substrates. Significantly, only those CV molecules that were chemically conjugated between the partially polarised silver nanoparticles and the underlying gold or silver substrates were found to show SERS under off-resonant conditions. The importance of partial charge transfer at the nanoparticle/capping agent interface and the resultant conjugation of CV molecules to off resonant SERS effects was confirmed by using gold nanoparticles prepared in a similar manner. In this case the capping agent binds to the nanoparticle through the amine group which does not facilitate charge transfer from the gold nanoparticle and under these conditions SERS enhancement in the sandwich configuration was not observed
Electrocatalytic and SERS activity of Pt rich Pt-Pb nanostructures formed via the utilisation of in-situ underpotential deposition of lead
The controlled synthesis of nanostructured materials remains an ongoing area of research, especially as the size, shape and composition of nanomaterials can greatly influence their properties and applications. In this work we present the electrodeposition of highly dendritic platinum rich platinum-lead nanostructures, where lead acetate acts as an inorganic shape directing agent via underpotential deposition on the growing electrodeposit. It was found that these nanomaterials readily oxidise at potentials below monolayer oxide formation, which significantly impacts on the methanol electrooxidation reaction and correlates with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis. Additionally these materials were tested for their surface enhanced Raman scattering (SERS) activity, where the high density of sharp tips provides promise for their application as SERS substrates