Electrode transition metal-containing

The complex phase diagrams and rich crystal chemistry of the transition metal-containing oxide systems, and great diversity in the defect chemistry and transport properties of mixed-conducting materials known in these systems, make it impossible to systematize all promising compositions in a brief survey. The primary attention here is therefore centered on the comparison of major families of the oxide mixed conductors used for dense ceramic membranes and porous electrodes of SOFCs and other high-temperature electrochemical devices. 

Electrogenerated PTs incorporating transition metal containing N,N -ethylenebis(salicylidenimine) (salen) complexes have been developed by the Reynolds group [203 04]. A polyalkyl ether chain bridging the phenyl rings in 97 creates an additional site for chelation of a second metal ion. A positive shift of the oxidation potential of poly(97) was observed in the presence of Li, Na, Mg " ", or Ba. These electrodes were also sensitive to Lewis bases such as pyridine and triphenylphosphine. 

Perspectives for fabrication of improved oxygen electrodes at a low cost have been offered by non-noble, transition metal catalysts, although their intrinsic catalytic activity and stability are lower in comparison with those of Pt and Pt-alloys. The vast majority of these materials comprise (1) macrocyclic metal transition complexes of the N4-type having Fe or Co as the central metal ion, i.e., porphyrins, phthalocyanines, and tetraazaannulenes [6-8] (2) transition metal carbides, nitrides, and oxides (e.g., FeCjc, TaOjcNy, MnOx) and (3) transition metal chalcogenide cluster compounds based on Chevrel phases, and Ru-based cluster/amorphous systems that contain chalcogen elements, mostly selenium. 

The photolytic reduction of N2 at TiO -suspensions was at first reported by Schrauzer et al. Small amounts of NH3 and N2H4 were obtained as products. The highest activity was found with anatase containing 20-30 % rutile. Very low yields were also obtained with p-GaP electrodes under illumination It is much easier to produce NH3 from NO -solutions at CdS- and Ti02-particles using S -ions as hole scavengers . Efficiencies are not reported yet. Recently the formation of NH3 from NO was observed at p-GaAs electrodes under illumination. In this case NH3-formation was only found in the presence of transition metal ions or their complex with EDTA. 

A variety of transition metal complexes including organometallics was subjected to an ac electrolysis in a simple undivided electrochemical cell, containing only two current-carrying platinum electrodes. The compounds (A) are reduced and oxidized at the same electrode. If the excitation energy of these compounds is smaller than the potential difference of the reduced (A ) and oxidized (A ) forms, back electron transfer may regenerate the complexes in an electronically excited state (A+ + A A + A). Under favorable conditions an electrochemiluminescence (eel) is then observed (A A + hv). A weak eel appeared upon electrolysis o t]jie following complexes Ir(III)-(2-phenylpyridine-C, N ) [Cu(I)(pyridine)i],... 

In the fifth paper of this chapter on cathodes, an investigation of thin-film oxide-hydroxide electrodes containing Cr, Ni, and Co compounds was authored by N. Vlasenko et al. The thin-films were produced by electrochemical deposition from transition metal aqueous fluorine-containing electrolytes onto steel substrates. These thin-films were tested in Li coin cells. Electrochemical activity appears to scale with the amount of fluoride used in the deposition the larger concentration of fluoride in the bath, the greater the capacity. One Ni oxide-hydroxide film electrode showed greater than 175 mAh/g reversible capacity on the 50th cycle with excellent coulombic efficiency. 

There are a number of ways of attaching a monolayer of redox molecules to an electrode surface.10 Multilayered films can be obtained by deposition of a polymer containing redox centers. These may be attached to the polymer backbone covalently, electrostatically, or coordinatively if the redox center contains a transition metal. 

The polymer CgoPt has also been made by using Pt(l,5-cyclooctadiene)2 [88], Various CjoM polymer films have been prepared by electrochemical reduction of transition metal complexes of the central metal Pd(II), Pt(II), Ir(I), Rh(l), Rh(ll), Rh(lll) and Au(l) [89, 90]. The metal complex in solution is first electrochemicaUy reduced to the zerovalent metal, which then forms polymer films containing M Coo on the electrode. 

A special case is when the electrochem-ically active components are attached to the metal or carbon (electrode) surface in the form of mono- or multilayers, for example, oxides, hydroxides, insoluble salts, metalloorganic compounds, transition-metal hexacyanides, clays, zeolites containing polyoxianions or cations, intercalative systems. The submonolayers of adatoms formed by underpotential deposition are neglected, since in this case, the peak potentials are determined by the substrate-adatom interactions (compound formation). From the ideal surface cyclic voltammetric responses, E° can also be calculated as... 

Mossbauer spectroscopy may be important and useful when applied to electrodes which contain ferromagnetic components. It is basically an in situ tool which provides valuable information on possible orientation and oxidation states of ferromagnetic species in the electrodes as a function of the electrochemical process and the potential applied. For example, electrodes for oxygen reduction may be highly catalytic when containing macrocycles with transition metal cations such as Fez+, Niz+, Coz+ [89,90], A typical apparatus for this technique is described in Ref. 91. 

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