Gold double layer

Bjerrum and coworkers have assigned the three rate maxima shown in Figs. 10.7 and 10.8 to (starting from the negative potential) (a) destruction of vanadium polymeric chains (b) electric double layer effect at gold working electrode (c) stabilization of V (V) vs V (IV). These explanations are very plausible. 

Mortari, A., Maaroof A., Martin, D. and Cortie, M.B. (2007) Mesoporous gold electrodes for measurement of electrolytic double layer capacitance. Sensors and Actuators B, 123, 262-268. 

Kunimatsu, K. and Bewick, A. (1986) Electrochemically modulated infrared spectroscopy of adsorbed water in the inner part of the double layer part 1. Oxygen-hydrogen stretching spectra of water on gold in 1M perchloric acid. fnd. J. Technol., 24, 407-412. 

The polycationic ammonium salt PEU can be chosen for increasing the ionic cloud in the electrical double layer, thus raising the electric repulsion between the gold particles in the sol. Small particles can be obtained (mean diameters between 3.1 and 4.2 nm) [24]. 

Zhong X, Yuan R, Chai Y, Liu Y, Dai J, Tang D (2005) Glucose biosensor based on self-assembled gold nanoparticles and double-layer 2d-network (3-mercaptopropyl)-trimethoxy-silane polymer onto gold substrate. Sensor Actuator B 104 191-198... 

Non-Aqueous Colloidal Metal Solutions. It has been difficult to prepare colloidal gold in non-aqueous media due to limitations in preparative methods (low salt solubilities, solvent reactivity, etc.), and the fact that the low dielectric constant of organic solvents has hindered stabilization of the particles. In aqueous solution the gold particles are stabilized by adsorption of innocent ions, such as chloride, and thus stabilized toward flocculation by the formation of a charged double layer, which is dependent on a solvent of high dielectric constant. Thus, it seemed that such electronic stabilization would be poor in organic media. 

Emersion has been shown to result in the retention of the double layer structure i.e, the structure including the outer Helmholtz layer. Thus, the electric double layer is characterised by the electrode potential, the surface charge on the metal and the chemical composition of the double layer itself. Surface resistivity measurements have shown that the surface charge is retained on emersion. In addition, the potential of the emersed electrode, , can be determined in the form of its work function, , since and represent the same quantity the electrochemical potential of the electrons in the metal. Figure 2.116 is from the work of Kotz et al. (1986) and shows the work function of a gold electrode emersed at various potentials from a perchloric acid solution the work function was determined from UVPES measurements. The linear plot, and the unit slope, are clear evidence that the potential drop across the double layer is retained before and after emersion. The chemical composition of the double layer can also be determined, using AES, and is consistent with the expected solvent and electrolyte. In practice, the double layer collapses unless (i) potentiostatic control is maintained up to the instant of emersion and (ii) no faradaic processes, such as 02 reduction, are allowed to occur after emersion. 

Preparation of Gold Nanocatalysts Supported on Silica Modified with Oxide Double Layers... 

Fig. 6-96. Change in differential capacity of an interfadal double layer leading or not leading to interfadal lattice transformation in anodic and cathodic potential sweeps for a gold electrode surface (100) in perchloric add solution Ey = critical potential beyond which the interfadal lattice transforms from (5 x 20) to (1 x 1) E = critical potential below which the interfadal lattice transforms from (1 x 1) to (5 x 20) Ejm = potential of zero charge VacE = volt referred to the saturated calomel electrode. [From Kolb-Schneider, 1985.]...

On the assumption of a somewhat mobile double layer, electrostatic attraction between particles may occur, due to this displacement effect, even if the total net charge be not zero, i.e. coagulation may take place before the isoelectric point is reached. The data of Zsigmondy on gold particles, and of Powis Zeit. Phys. Ohem. Lxxxix 186, 1915) on oil particles, have indeed shown that the optimum point for precipitation is not actually at the isoelectric point, although in the case of gold, practically complete discharge of the double layer had to take place before coalescence. 

Marinkovic et al. [50] have used in situ IR reflection spectroscopy to study adsorption of nitrate ions on Au(lll) electrodes. The ions were bonded to the gold surface via one of their oxygen atoms. Within the double-layer N03 formed contact ion pairs with hydronium ions. The extent of this process depended on the applied potential. 

Using reflectometry, Barten etal. [259] have investigated adsorption of quater-nized poly-2-vinyl pyridine, of a fixed charge per monomer, on a gold electrode. The total adsorbed amount of the compound decreased linearly with the double-layer potential of gold. Adsorption proceeded up to a relatively high doublelayer potential and was accompanied by a relatively high contribution of nonelectro-static interactions. 

In recent years, Burke and coworkers have found [373] that severe cathodization of pc-Au in acid solution resulted in the appearance of faradaic responses in the double-layer region. Such anomalous behavior may be explained by the presence of active gold atoms on the electrode surface. These active atoms appear as a result of the pretreatment process, when the part of inserted energy into the gold sample is retained mosdy by the surface atoms and atoms of the outer layers, in the form of various types of defects, for example, adatoms, vacancies, grain boundaries, and others. 

Controlled reduction of cadmium (or lead) ions on surfaces of nanosized silver (or gold) metallic particles results in the formation of double-layer colloids [532-534]. Depending on the coverage, the second layer can vary from being non-metallic clusters to quasi-metallic and metallic colloids. Growth of the second-layer particles can be monitored by absorption spectrophotometry. For... 

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