Metal electrodes electrocatalytic activity

In acid electrolytes, carbon is a poor electrocatalyst for oxygen evolution at potentials where carbon corrosion occurs. However, in alkaline electrolytes carbon is sufficiently electrocatalytically active for oxygen evolution to occur simultaneously with carbon corrosion at potentials corresponding to charge conditions for a bifunctional air electrode in metal/air batteries. In this situation, oxygen evolution is the dominant anodic reaction, thus complicating the measurement of carbon corrosion. Ross and co-workers [30] developed experimental techniques to overcome this difficulty. Their results with acetylene black in 30 wt% KOH showed that substantial amounts of CO in addition to C02 (carbonate species) and 02, are... 

Although several metals, such as Pt and Ag, can also act as electrocatalysts for reaction (3.7) the most efficient electrocatalysts known so far are perovskites such as Lai-xSrxMn03. These materials are mixed conductors, i.e., they exhibit both anionic (O2 ) and electronic conductivity. This, in principle, can extend the electrocatalytically active zone to include not only the three-phase-boundaries but also the entire gas-exposed electrode surface. 

A third way to increase both the active surface area and the number of oxygenated species at the electrode surface is to prepare alloy particles or deposits and then to dissolve the non-noble metal component. This technique, which is similar to that used to prepare Raney-type catalysts, yields very high surface area electrodes and hence some improvements in the electrocatalytic activities compared with those of pure platinum. However, it is always difficult to be sure whether the mechanism of enhancment of the activities is due to this effect or the possible presence of remaining traces of the dissolved metal. Results with PtyCr and PtSFe were encouraging, although the effect of iron is still under discussion. From studies in a recent work on the behavior of R-Fe particles for methanol electrooxidation, it was concluded that the electrocatalytic effect is due to the Fe alloyed to platinum. ... 

The second most widely used noble metal for preparation of electrodes is gold. Similar to Pt, the gold electrode, contacted with aqueous electrolyte, is covered in a broad range of anodic potentials with an oxide film. On the other hand, the hydrogen adsorption/desorption peaks are absent on the cyclic voltammogram of a gold electrode in aqueous electrolytes, and the electrocatalytic activity for most charge transfer reactions is considerably lower in comparison with that of platinum. 

L. D. Burke, J. A. Collins, M. A. Horgan, L. M. Hurley, and A. P. O Mullane, The importance of the active states of surface atoms with regard to the electrocatalytic behaviour of metal electrodes in aqueous media, Electrochim. Acta 45, 4127 134 (2000). 

It was found that the electrocatalytic activity strongly depends on the nature of the electrode it decreases in the order Rh > Ru > Ir > Pd and Pt for the transition-metal electrodes and in the order Cu > Ag > Au for the coinage metals. It was concluded that the rate-determining step on Ru, Rh, Ir, Pt, Cu, and Ag is the reduction of nitrate to nitrite. It was assumed that chemisorbed nitric oxide is the key surface intermediate in the nitrate reduction. It was suggested that ammonia and hydroxylamine are the main products on transition-metal electrodes. This is in agreement with the known mechanism for NO reduction, which forms N2O or N2 only if NO is present in the solution. On Cu the production of gaseous NO was found, which was explained by the weaker binding of NO to Cu as compared to the transition metals. 

In [105], a reduction procedure involving the permeation of hydrogen through palladized Pd sheet electrodes is described. The electrocatalytic activity of various metal (Ti, Zr, Nb, No, Fe, Ni,... 

Platinum electrodes are widely used as an inert electrode in redox reactions because the metal is most stable in aqueous and nonaqueous solutions in the absence of complexing agents, as well as because of its electrocatalytic activity. The inertness of the metal does not mean that no surface layers are formed. The true doublelayer (ideal polarized electrode) behavior is limited to ca. 200-300 mV potential interval depending on the crystal structure and the actual state of the metal surface, while at low and high potentials, hydrogen and oxygen adsorption (oxide formation) respectively, occur. 

Metallic NPs are most widely used in catalytic applications due to their inherent properties. Several examples of platinum and gold NPs are apparent in the literature. For example, electrodeposited platinum NPs on porous carbon substrates exhibit electrocatalytic activity for the oxidation of methanol.60 In another example, gold NPs catalyze the electrochemical oxidation of nitric oxide on modified electrodes.61 In general, catalytic NPs provide two distinct functions enhancing an electrochemical reaction and/or increasing electron transfer to an electrode. 

There are certain combinations of electrode materials, solvents and operating conditions, which allow the reduction of C02 to afford hydrocarbons. It was concluded in a comparative study using many different metal electrodes in aqueous KHCO3 solution that either CO (Ag, Au) or formic acid (In, Sn, Hg, Pb) are produced as a result of the reduction of C02, and Cu has the highest electrocatalytic activity for the production of hydrocarbons, alcohols, and other valuable products.137 Most of the studies, since the mid-1990s, consequently, have focused on the further elucidation of electrocatalytic properties of copper. 

Commercial catalytic hydrogenations of unsaturated compounds use Raney nickel or—less commonly—Pt catalyst supported on active carbon. Electrocatalytic hydrogenation can be performed at platinized platinum or other platinum-metal electrodes. Adsorbed hydrogen atoms are the active reactant in catalytic as well as in electrocatalytic hydrogenation. 

Electrocatalytic Activity of Semiconductor Electrodes Modified by Surface-Deposited Metal Nanophase... 

On examination of the electrocatalytic activity of metal nanoparticles in dark electrode processes, of significant interest is the appearance of the limiting current on the i,V curve for the Cu-modified Ti02 electrode, especially taking into account that it does not depend on the stirring of electrolyte and cannot be considered as a consequence of any diffusion limitation caused by the electrolyte solution. At the same time, this limiting current is very sensitive to the heating of the electrolyte as well as to the IR illumination of the electrode. 

To understand the above peculiarities of the electrocatalytic activity of metal nanophase in dark oxidation processes on the Ti02 electrodes, one should take into account the differences in the inherent electrocatalytic properties of deposited metals, on the one hand, and the data on the electronic states formed by the nanoparticles of these metals in a band gap of Ti02 electrode, on the other hand. A peculiar shape of i,V-curves obtained for... 

From the above reasoning one could expect that the pre-deposition of small amounts of noble metals on the Ti02 surface in a form of the intermediate sub-layer, which can induce the electroactive electronic surface states in the Ti02 band gap, may enhance the electrocatalytic effect of subsequently deposited Cu particles. Actually, the photocatalytic deposition of silver particles in amount of 5xl014 atoms/cm-2, which on its own only slightly increases the electrocatalytic activity of Ti02 electrode, leads to 2-3-fold enhancement of the electrocatalytic activity of Cu particles subsequently deposited in a relatively high concentration (1016-1017 atoms/cm 2) [52],... 

In a similar manner, during the process of the existing metal particles growth and the deposition of new species using cathodically biased electrode in a solution of metal ions, the growing metal phase will be also localized at the sites of the surface exposure of the continuous donor centers. The reason for this is that namely these sites possess substantially enhanced electrocatalytic activity in comparison with the stoichiometric oxide surface and exhibit the properties of current channels non-restricted by the Schottky barrier at the interface with the electrolyte. Actually, a peculiar decoration of the sites of donor centers accumulation and donor clusters localization by the metal nanoparticles takes place in the dark processes of metal particle deposition onto the surface of the chemically inert wide-band-gap oxides. The increased electrocatalytic activity of the wide-band-gap semiconductor electrodes resulted from the deposition of metal nanoparticles on their surface may be also regarded as a kind of such decoration . 

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