Exploring the applications of a pulsating jet hydrodynamic modulated voltammetric (HMV) system - electrochemistry of nanostructured Pt electrodes and trace analysis

The electrochemistry of nanostructured electrodes is investigated using hydrodynamic modulated voltammetry (HMV). Here a liquid crystal templating process is used to produce a platinum modified electrode with a relatively high surface area (Roughness factor, Rf = 42.4). The electroreduction of molecular oxygen at a nanostructured platinum surface is used to demonstrate the ability of HMV to discriminate between Faradaic and non-Faradaic electrode reactions. The HMV approach shows that the reduction of molecular oxygen shows considerable hysteresis correlating with the formation and stripping of oxide species at the platinum surface. Without the HMV analysis it is difficult to discern the same detail under the conditions employed. In addition the detection limit of the apparatus is explored and shown, under ideal conditions, to be of the order of 45 nmol dm(-3) employing [Fe(CN)(6)](4-) as a test species. (C) 2009 Elsevier B.V. All rights reserved.

Electrochemical characterisation and anodic stripping voltammetry at mesoporous platinum rotating disc electrodes

Using the technique of liquid crystal templating a rotating disc electrode (RDE) was modified with a high surface area mesoporous platinum film. The surface area of the electrode was characterised by acid voltammetry, and found to be very high (ca. 86 cm(2)). Acid characterisation of the electrode produced distorted voltammograms was interpreted as being due to the extremely large surface area which produced a combination of effects such as localised pH change within the pore environment and also ohmic drop effects. Acid voltammetry in the presence of two different types of surfactant, namely Tween 20 and Triton X-100, suggested antifouling properties associated with the mesoporous deposit. Further analysis of the modified electrode using a redox couple in solution showed typical RDE behaviour although extra capacitive currents were observed due to the large surface area of the electrode. The phenomenon of underpotential deposition was exploited for the purpose of anodic stripping voltammetry and results were compared with data collected for microelectrodes. Underpotential deposition of metal ions at the mesoporous RDE was found to be similar to that at conventional platinum electrodes and mesoporous microelectrodes although the rate of surface coverage was found to be slower at a mesoporous RDE. It was found that a mesoporous RDE forms a suitable system for quantification of silver ions in solution.

Lag-time effects on a naturally ventilated large thermometer screen

Systematic natural ventilation effects on measured temperatures within a standard large wooden thermometer screen are investigated under summer conditions, using well-calibrated platinum resistance thermometers. Under low ventilation (2mwind speed u2 < 1.1 m s−1), the screen slightly underestimates daytime air temperature but overestimates air temperature nocturnally by 0.2◦C. The screen’s lag time L lengthens with decreasing wind speed, following an inverse power law relationship between L and u2. For u2 > 2 m s−1, L ∼ 2.5 min, increasing, when calm, to at least 15 min. Spectral response properties of the screen to air temperature fluctuations vary with wind speed because of the lag changes. Ventilation effects are particularly apparent at the higher (>25◦C) temperatures, both through the lag effect and from solar heating. For sites where wind speed decreases with increasing daytime temperature, thermometer screen temperatures may consequently show larger uncertainties at the higher temperatures. Under strong direct beam solar radiation (>850W m−2) the radiation effect is likely to be <0.4◦C. Copyright c 2011 RoyalMeteorological Society