Cobalt based coatings as catalysts for methanol oxidation

The cobalt based coatings with refractory metals (Mo, W, Zr) were deposited from pyrophosphate-citrate electrolytes in a pulsed mode. It has been shown that, with increasing current density, Co-Mo-W and Co-W-ZrO2 alloys are enriched in tungsten, grain sizes decrease, but a network of cracks appears on the surface of the Co-Mo-W coating. In the Co-Mo-ZrO2 coating, with increasing current density, the zirconium content increases due to molybdenum, and the surface is the most fractured and small-globular. The surface roughness parameters for Co-Mo-ZrO2 are one order of magnitude higher than those for Co-Mo-W. Cyclic voltammograms show that the Co-Mo-ZrO2 deposits are characterized by the highest stability under anodic polarization due to the inclusion of molybdenum and zirconium(IV) oxide in their composition. The kinetics of the methanol anodic oxidation on electrodes coated with cobalt alloys was studied, and the participation of intermediate metal oxides in oxygen transport was revealed. A significant increase in the anode current peak indicates a higher electro-catalytic activity of the zirconium-containing coatings among the studied alloys.