Cathodes useful in an electrolytic cell, such as a chlor-alkali cell, are disclosed which have a metallic-surfaced substrate coated with a catalytic coating composition. In one aspect, the catalytic coating includes a base layer of at least one primary electrocatalytic metal with particles of at least one electrocatalytic metal oxide entrapped therein. In another aspect, at least one upper oxide layer is formed on the base layer. Each upper oxide layer includes a substantially heterogeneous mixture of at least one primary electrocatalytic metal oxide and at least one secondary electrocatalytic metal oxide. The catalytic coatings are tightly adherent to the underlying substrate, resist loss during cell operation and exhibit low hydrogen overvoltage potentials. Also disclosed are methods for preparing the cathodes.
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