Thermal Oxides DSA

For a long time, conventional alkaline electrolyzers used Ni as an anode. This metal is relatively inexpensive and a satisfactory electrocatalyst for O2 evolution. With the advent of DSA (a Trade Name for dimensionally stable anodes) in the chlor-alkali industry [41, 42[, it became clear that thermal oxides deposited on Ni were much better electrocatalysts than Ni itself with reduction in overpotential and increased stability. This led to the development of activated anodes. In general, Ni is a support for alkaline solutions and Ti for acidic solutions. The latter, however, poses problems of passivation at the Ti/overlayer interface that can reduce the stability of these anodes [43[. On the other hand, in acid electrolysis, the catalyst is directly pressed against the membrane, which eliminates the problem of support passivation. In addition to improving stability and activity, the way in which dry oxides are prepared (particularly thermal decomposition) develops especially large surface areas that contribute to the optimization of their performance. 

Oxide surfaces are high-energy surfaces that interact with water molecules becoming covered by a carpet of OH groups. The latter, in contact with aqueous solutions, behave as weak acids or weak bases, giving rise to dissociation that is the main origin of surface charging  

Whereas Pt in an acidic solution saturated with H2 acquires the reversible potential of the hydrogen electrode, this is not the case for the same Pt electrode in an acidic solution saturated with O2. This is related to the high activation energies involved in breaking and forming chemical bonds. Thus the O2 reaction is known to be highly irreversible. In particular, a Pt electrode in 02-saturated solution acquires a potential 0.9V (SHE) rather than 1.23 V. Hence an overpotential of 0.3 V can already be expected from an analysis of the equilibrium conditions. 

of course, not a good electrocatalyst for the O2 evolution reaction, although it is the best for the O2 reduction reaction. However, also with especially active oxides of extended surface area, the theoretical value of E° has never been observed. For this reason, the search for new or optimized materials is a scientific challenge but also an industrial need. A theoretical approach to O2 electrocatalysis can only be more empirical than in the case of hydrogen in view of the complexity of the mechanisms. However, a chemical concept that can be derived from scrutiny of the mechanisms mentioned above is that oxygen evolution on an oxide can be schematized as follows [59]  

As an oxide is polarized anodically, it is first oxidized to an unstable higher oxide whose rapid decomposition gives back the original oxide with liberation of O2. This is a chemical view of a cycle whose feasibility is governed by the AHj of transition from the lower to the higher oxide. Such a AH plays the role of AHads(OH) [the analogous of AHads(H) for the H2 reaction]. 

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