Anode ruthenium oxide/titanium dioxide

Because of the considerable corrosivity of chlorine toward most metals, anodic chlorine evolution can only be realized for a few electrode materials. In industry, graphite had been used primarily for this purposes in the past. Some oxide materials, manganese dioxide for instance, are stable as well. At present the titanium-ruthenium oxide anodes (DSA see Chapter 28) are commonly used. 

Titanium dioxide is a catalytically inactive but rather corrosion-resistant material. Ruthenium dioxide is one of the few oxides having metal-like conductivity. It is catalytically quite active toward oygen and chlorine evolution. However, its chemical stability is limited, and it dissolves anodically at potentials of 1.50 to 1.55 V (RHE) with appreciable rates. A layer of mixed titanium and ruthenium dioxides containing 1-2 mg/cm of the precious metal has entirely unique properties in terms of its activity and selectivity toward chlorine evolution and in terms of its stability. With a working current density in chlorine evolution of 20 to 50mA/cm, the service life of such anodes is several years (up to eight years). 

Direct electrooxidation is theoretically possible at low potentials, before oxygen evolution, but the reaction rate usually has low kinetics that depends on the electro-catalytic activity of the anode. High electrochemical rates have been observed using noble metals such as Pt and Pd, and metal-oxide anodes such as iridium dioxide, ruthenium-titanium dioxide, and iridium-titanium dioxide (Foti et al. 1997). 

The electrocatalytic behavior of olefins was studied by Zanta et al. (2000) at thermally prepared ruthenium-titanium- and iridium-titanium-dioxide-coated anodes. The aliphatic olefins were shown to be inactive in the region before oxygen evolution, while aromatic ones showed one or two oxidation peaks, and the catalytic activity seemed to be the same for both substrates. However, as for platinum anodes, voltammetric studies and FTIR analyses have also shown the formation of a polymeric film that blocks the surface of the electrode and decreases its activity. 

The DSA-type anodes are inert , coated anodes made of a valve metal (titanium, niobium, or tantalum) base coated with an electrochemically active coating. The active coating is made either of noble metals or of mixed metal oxides. Noble metals in active coatings are usually platinum or platinum alloys. Mixed metal-oxide coatings contain active oxides and inert oxides the active components are usually ruthenium dioxide (R.UO2) and iridium dioxide (IrC>2) and the inert components are mostly titanium dioxide (TiC>2) and other oxides such as tantalum... 

Recently it has been shown that the oxides of the platinum metals can have a higher corrosion resistance than the metals themselves , and have sufficient conductivity to be used as coatings for anodes, e.g. with titanium cores. Anodes with a coating of ruthenium dioxide are being developed for use in mercury cells for the electrolysis of brine to produce chlorine , since they are resistant to attack if in contact with the sodium-mercury amalgam. 

ORTA — refers to an oxidized ruthenium titanium anode (ORTA) whereby a titanium substrate is covered by ruthenium dioxide. ORTA is the term commonly encountered in the Russian literature, whereas the term -> dimensionally stable electrode (anode) (DSA) is used in the English literature [i] (although DSA can also refer to a Ti substrate covered with a multi-metal... 

Dimensionally Stable Anodes— These anodes are composed of a base metal such as titanium, coated with a precious metal oxide (e.g., ruthenium dioxide). Such anodes can be used instead of Pt or carbon for oxygen evolution counter electrodes in an organic electrosynthesis. They have also found some applications for organic oxidation reactions [61]. 

Oxide-metal composite anodes consist of a mixed ruthenium dioxide and titanium oxide coating sintered onto a commercially pure titanium substrate. These expanded-mesh anodes also are used for protecting reinforcing steel in concrete [37]. 

Platinum anodes have a limited operational range of oxidation potentials and thus attention has focused on Sn02-coated titanium materials. The tin oxide material, when doped with Sb (approximately 5%) to impart the appropriate electrical conductivity, has oxygen overpotentials some 600 mV greater than those of platinum. Tin oxide gives higher oxidation efficiencies to those of platinum, lead dioxide, ruthenium and iridium oxide (DSA) electrodes and is reported to be stable to corrosion during anodic oxidation. 

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