Platinum electrodes metal deposition methods

To prepare metal hexacyanoferrate films, very frequently the following procedure was followed first a film of the respective metal, for example, cadmium [79], copper [80], silver [81], or nickel [82, 83] was elec-trochemically plated on the surface of a platinum electrode, and that was followed by chemical oxidation of the metal film in a solution of K3[Fe(CN)6], leading to the formation of the metal hexacyanoferrates. The same method has been used to produce films of nickel hexacyanoruthen-ate and hexacyanomanganate using the appropriate anions [83]. It is also possible to perform the oxidation of the deposited metals in solutions containing hexacyano-ferrate(II) by cyclic oxidation/reduction of the latter. In a similar way, films of copper heptacyanonitrosylferrate have been deposited [84]. 

In electrogravimetry [19], the analyte, mostly metal ions, is electrolytically deposited quantitatively onto the working electrode and is determined by the difference in the mass of the electrode before and after the electrolysis. A platinum electrode is usually used as a working electrode. The electrolysis is carried out by the con-trolled-potential or the controlled-current method. The change in the current-potential relation during the process of metal deposition is shown in Fig. 5.33. The curves in Fig. 5.33 differ from those in Fig. 5.31 in that the potentials at i=0 (closed circles) are equal to the equilibrium potential of the M +/M system at each instant. In order that the curves in Fig. 5.33 apply to the case of a platinum working electrode, the electrode surface must be covered with at least a monolayer of metal M. Then, if the potential of the electrode is kept more positive than the equilibrium potential, the metal (M) on the electrode is oxidized and is dissolved into solution. On the other hand, if the potential of the electrode is kept more negative than the equilibrium potential, the metal ion (Mn+) in the solution is reduced and is deposited on the electrode. 

Tire electrical method, commonly applied to the preparation of colloidal metals, can also be extended to selenium. When an electric discharge is made to pass under pure water between a platinum anode and a cathode prepared by fusing a small piece of selenium on to platinum foil, colloidal selenium is slowly formed.6 When a dilute solution of selenious anhydride is electrolysed using platinum electrodes, a colloidal solution of selenium and a black cathodic deposit of selenium... 

The processability of certain CEPs has been utilized in the construction of microsystems, particularly miniature sensor systems. For example, simply dip-coating connecting platinum wires with a polyaniline formulation produces a useful humidity sensor.133 CEPs can also be screen-printed or ink-jet-printed to produce the complex shapes needed for various devices. Electrodeposition of CEPs is also a popular processing method, and this technique is compatible with conventional MEMS fabrication, where lithography and etching can be used to prepattern metal electrodes. Subsequent deposition of CEP by electrochemical polymerization produces the CEP microdevice.129... 

Ruthenium and osmium depositions on platinum are of special interest with reference to methanol anodic oxidation on fuel cells and were first reported in the early 1960s [116,117], Among the different methods of deposition of ruthenium or osmium on platinum [116-121], the spontaneous deposition method is attractive because of its simplicity and the fast achievement of a surface concentration plateau (reached in seconds) [26,122,123]. Contrary to the reversible behavior of the electrochemically deposited ruthenium on noble metal substrates, the films formed by spontaneous deposition normally do not dissolve easily from the metal surface. They are very stable and normally change to stable hydroxides and oxides when the electrode potential is increased. 

To improve the electrocatalytic activity of platinum and palladium, the ethanol oxidation on different metal adatom-modified, alloyed, and oxide-promoted Pt- and Pd-based electrocatalysts has been investigated in alkaline media. Firstly, El-Shafei et al. [76] studied the electrocatalytic effect of some metal adatoms (Pb, Tl, Cd) on ethanol oxidation at a Pt electrode in alkaline medium. All three metal adatoms, particularly Pb and Tl, improved the EOR activity of ft. More recently, Pt-Ni nanoparticles, deposited on carbon nanofiber (CNE) network by an electrochemical deposition method at various cycle numbers such as 40, 60, and 80, have been tested as catalysts for ethanol oxidadmi in alkaline medium [77]. The Pt-Ni alloying nature and Ni to ft atomic ratio increased with increasing of cycle number. The performance of PtNi80/CNF for the ethanol electrooxidation was better than that of the pure Pt40/CNF, PtNi40/CNF, and PtNi60/CNF. 

One of the earliest applications of the template method was to prepare ensanble miCTo-scopic (7, 18) and nanoscopic electrodes (116, 141). Such electrodes were prepared by electrochemically depositing noble metals within the pores of the commercially available polymeric filtration membranes. The fabrication of a microelectrode ensemble based on the electrochemical deposition of platinum into the pores of a track-etched microporous polycarbonate host membrane was first shown in 1987 by Charles Martin (7). The word ensemble was used to describe the final device because the elements in the device are not evenly spaced. The procedure is simple, and requires only routine and inexpensive electrochemical instrumentation. It was ultimately found that electroless plating allowed for more uniform metal deposition (116). Both plating methods are important for the fabrication of the array, and further considerations continue in the following. 

Controlled-potential coulometric methods have been applied to more than fifty elements in inorganic com-pounds. Historically, mercury was widely used as the working electrode material, and methods for the deposition of two dozen or more metals at this electrode have been described. In recent years, many other electrode materials have been used, including platinum and various forms of carbon. Coulometry is used widely in the nuclear energy field for the relatively interference-free determination of uranium and plutonium. For example, the uranium-to-oxygen ratio in spent nuclear fuel has been determined by controlled-potential coulometry with a precision of 0.06% relative standard deviation (RSD). ... 

Electrogravimetry is one of the oldest electroanalytical methods and generally consists in the selective cathodic deposition of the analyte metal on an electrode (usually platinum), followed by weighing. Although preferably high, the current efficiency does not need to be 100%, provided that the electrodeposition is complete, i.e., exhaustive electrolysis of the metal of interest this contrasts with coulometry, which in addition to exhaustive electrolysis requires 100% current efficiency. 

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