Platinum electrodes underpotential

Santos MC, Machado SAS (2004) Microgravimetric, rotating ring-disc and voltammetric studies of the underpotential deposition of selenium on polycrystalline platinum electrodes. J Electroanal Chem 567 203-210... 

Clavilier J, Feliu JM, Aldaz A. 1988. An irreversible structure sensitive adsorption step in bismuth underpotential deposition at platinum electrodes. J Electroanal Chem 243 419-433. 

In some cases, the electrode material is the limiting factor of the electrochemical stability window. In a metal salt solution, underpotential deposition (UPD) may occur. In some examples, such as gold or platinum electrodes in the presence of lithium ions, the UPD appears at potentials that are substantially higher than the bulk metal deposition [4-6], In addition, some metals may possess catalytic activity for specific reduction or oxidation processes [7-12], Many nonactive metals (distinguished from the noble metals), including Ni, Cu, and Ag, which are commonly used as electrode materials, may dissolve at certain potentials that are much lower than the oxidation potentials of the solvent or the salt. In addition, some electrode materials may be catalytic to certain oxidation or reduction processes of the solution components, and thus we can see differences in the stability limits of nonaqueous systems depending on the type of electrode used. 

The Cat, or its product of electrode oxidation or reduction Cat, is immobilized at the electrode surface and decreases the overpotential for oxidation or reduction of the S, without being involved in the chemical redox reaction with the S. Typical example is the catalytic effect of underpotential deposited layer of lead on a platinum electrode, on anodic oxidation of methanol [v]. 

A phenomenon similar to the underpotential deposition of metals is also observed in the study of the anodic oxidation of halides. In Fig. 81 we show the dependence of current on potential during an anodic potential sweep obtained on a platinum electrode in a nonaauenns mpdinm A current peak corresponding to the formation of atomic bromine on the surface is observed, about 0.4 V before the potential for formation of molecular bromine is reached. The two reactions considered ... 

This rather simple experiment demonstrates quite clearly the poisoning of the oxygen reduction process by copper. Incidentally, Cu(II) is a rather common impurity in distilled water and mineral acids, and this experiment demonstrates that underpotential deposition of a monolayer of copper from solutions containing as little as 1 ppm Cu can drastically affect the behavior of a platinum electrode. Adsorption of small amounts of other impurities (i.e., organic molecules) can also have an effect on solid-electrode behavior. Thus, electrochemical experiments often require making great efforts to establish and maintain solution purity. 

The spectra show two resonances located around 2065 cm and 1965 cm . The first corresponds to linearly bound CO, the latter was assigned to CO in a bridge-bound position [786]. The conversion of CO in a bridging location into species atop has been identified with SFG [794]. The combination of the high light intensity (e.g. free-electron lasers) and the possibility to obtain absolute spectra without any modulation technique has allowed the detection of generally weak bands like those of over- and underpotential deposited hydrogen on a platinum electrode [795, 796]. Studies of coadsorption of cyanide anions and cetylpyridinium cations on Au(l 11) and Au(210) revealed marked differences [797]. CN is bound... 

Xia XH, Iwasita T (1993) Influence of underpotential deposited lead upon the oxidation of HCOOH in HCIO4 at platinum electrodes. J Electrochem Soc 140 2559—2565... 

Zolfaghari, A., Chayer, M. and Jerkiewicz, G. (1997) Energetics of the underpotential deposition of hydrogen on platinum electrodes. 1. Absence of coadsorbed species. Journal of the... 

The catalytic properties of a Pt/Sn combination were observed on different kinds of electrode materials alloys [90], electro co-deposits of Pt and Sn [89, 90], underpotential deposited tin [42] or a mixture of tin oxide and platinum deposited on glass [95], All different materials present a marked influence on methanol electrooxidation. 

In this paper we report the application of bimetallic catalysts which were prepared by consecutive reduction of a submonolayer of bismuth promoter onto the surface of platinum. The technique of modifying metal surfaces at controlled electrode potential with a monolayer or sub-monolayer of foreign metal ("underpotential" deposition) is widely used in electrocatalysis (77,72). Here we apply the theory of underpotential metal deposition without the use of a potentiostat. The catalyst potential during promotion was controlled by proper selection of the reducing agent (hydrogen), pH and metal ion concentration. 

Pitner and Hussey studied the electrochemistry of tin in acidic and basic AICI3/I-ethyl-3-methyl-imidazolium chloride-based ionic liquids by using voltammetry and chronoamperometry at 40 °C [15]. They reported that the Sn(II) reduction process is uncomplicated at a platinum substrate, where in the atidic ionic liquid the reduction wave was observed at +0.46 V on the Pt electrode and the oxidation at +0.56 V. When they used a gold electrode instead of platinum, they observed an underpotential deposition of a tin monolayer and an additional underpotential deposition process that was attributed to the formation of tin-gold alloy at the surface. The deposition of tin on glassy carbon was controlled by nudeation. 

Noble metal electrodes include metals whose redox couple M/Mz+ is not involved in direct electrochemical reactions in all nonaqueous systems of interest. Typical examples that are the most important practically are gold and platinum. It should be emphasized, however, that there are some electrochemical reactions which are specific to these metals, such as underpotential deposition of lithium (which depends on the host metal) [45], Metal oxide/hydroxide formation can occur, but, in any event, these are surface reactions on a small scale (submonolayer -> a few monolayers at the most [6]). 

Cathodic deposition of magnesium from various chloride melts on different substrates has been studied by several authors [288-290], In dilute solutions of Mg(II) species the cathode process has been found to be controlled by diffusion of the reactant. Alloy formation has been observed on platinum, as reported by Tunold [288] and Duan et al. [290], The rate constant of the charge transfer process on a Mg/Ni electrode in molten NaCl-CaCl2-MgCl2 was reported by Tunold to have a value of about 0.01 cm s 1. This author also reported underpotential deposition of a monolayer on iron electrodes, at potentials approximately 100 mV positive to the Mg deposition potential. 

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