Cathode coating catalytic

The cathode in diaphragm and membrane cells has been steel where the hydrogen overpotential is about 400 mV. Coatings of nickel alloys are now available which decrease this overpotential to 150—200 mV and there are expectations that improvements in the catalytic coating will reduce it further to 20—50 mV. Such cathode coatings will again substantially improve the energy consumption of the industry. 

The cathode material is carbon steel in diaphragm cells, and nickel, often with a catalytic coating in membrane cells. As discussed in Section 4.6.6, exposure to anolyte containing active chlorine (CI2. HOCl, and OCl ) without cathodic protection is the primary reason for the corrosion of these components, unless the cathode coating is pore-free and noble metal based. Another species contributing to the corrosion of iron and nickel is the hydroxyl ion in the catholyte. 

Catalytic cathodes in membrane cell operations exhibit a voltage savings of 100—200 mV and a life of about 2 + yr using ultrapure brine. However, trace impurities such as iron from the caustic recirculation loop can deposit on the cathode and poison the coating, thereby reducing its economic life. 

A similar catalytic activity with a monomeric porphyrin of iridium has been observed when adsorbed on a graphite electrode.381-383 It is believed that the active catalyst on the surface is a dimeric species formed by electrochemical oxidation at the beginning of the cathodic scan, since cofacial bisporphyrins of iridium are known to be efficient electrocatalysts for the tetraelectronic reduction of 02. In addition, some polymeric porphyrin coatings on electrode surfaces have been also reported to be active electroactive catalysts for H20 production, especially with adequately thick films or with a polypyrrole matrix.384-387... 

Electrocatalytic hydrogenation has the advantage of milder reaction conditions compared to catalytic hydrogenation. The development of various electrode materials (e.g., massive electrodes, powder cathodes, polymer film electrodes) and the optimization of reaction conditions have led to highly selective electrocatalytic hydrogenations. These are very suitable for the conversion of aliphatic and aromatic nitro compounds to amines and a, fi-unsaturated ketones to saturated ketones. The field is reviewed with 173 references in [158]. While the reduction of conjugated enones does not always proceed chemoselectively at a Hg cathode, the use of a carbon felt electrode coated with polyviologen/Pd particles provided saturated ketones exclusively (Fig. 34) [159]. 

Saturating the electrolyte with iron(lll) hydroxide (e.g., by addition of aqueous solutions of ferric nitrate) and simultaneously adding cobaltous salts leads to in situ formation of a mixed Fe(llI)/Co(ll)/Co(IIl) deposit, which exhibits catalytic activity comparable to that of Fe304 shown by the current voltage curve in Fig. 11. Such mixed oxidic catalyst coatings are composed of very small oxide crystals, which evidently are dissolved upon current interruption due to dissociative oxide dissolution. The transfer of dissolved metal ions to the cathode followed by cathodic deposition of the metal, however, can be completely prohibited, if the potential of the cathode due to optimal electrocatalysis of cathodic hydrogen evolution proceeds with an over-... 

Microscopic and spectroscopic investigations (SEM and XPS) reveal the relatively fast change of the chemical composition of nickel sulfide coatings upon the onset of cathodic hydrogen evolution (74). Indeed, at 90°C all nickel sulfide phases are reduced to porous nickel within several days to a week s time. They lose some catalytic activity with time with an increase in overvoltage between 0.15 and 0.3 V after continuous operation for 1 year. It is clear that the catalyst after I week is already no longer nickel sulfide but some type of Raney nickel. Thus far the initial catalytic activity of the NiS, coating is of little relevance. The respective results and data are due to be published by the present authors (73). 

The cell anode and cathode spaces are separated by a solid-state electrolyte membrane. The anode is made of a porous, water-penetrable and current-conductive carrier material coated with an active layer. At the site where the active catalytic layer and the electrolyte membrane touch ozone is produced when a direct current of 3 to 6 V at currents of up to 50 A (corresponding with a current intensity of 0.2 to 3.0 A cm-2) are applied (Fischer, 1997). 

Ni can be taken as the reference material against which all other materials should be evaluated. On the average, the operating overpotential of untreated Ni electrodes is about 0.4 V at 0.2 A cm-2 [5], Beyond Ni, we deal with activated cathodes , which in fact derive from the idea of activated anodes such as the DSA . By activated electrodes we mean that the surface has been subjected to some treatments aimed at increasing its catalytic activity. This can be a treatment which modifies the surface structure and the morphology of the base metal, but more often the treatment is aimed at coating the base metal with a more active material [31]. 

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