Electrodeposition of Crystalline Co 3O 4-A Catalyst for the Oxygen Evolution Reaction


Crystalline films of Co 3O 4 are deposited by electrochemically oxidizing a tartrate complex of Co 2+ in an aqueous, alkaline solution at elevated temperatures. The crystallinity and stability of the films are a strong function of the deposition temperature. Films deposited at temperatures from 50 to 90 °C are amorphous, but films deposited from refluxing solution at 103 °C are crystalline. The crystalline films adhere strongly to the substrate, whereas the amorphous films peel off of the substrate when dried due to drying stresses. The crystalline films deposit with the normal spinel structure, with a lattice parameter of 0.8097 nm and crystallite size of 26 nm. The catalytic activity of Co 3O 4 for the oxygen evolution reaction (OER) of the crystalline and amorphous films is compared by Tafel analysis in alkaline solution at pH 14. The crystalline Co 3O 4 film has a Tafel slope of 49 mV/decade and an exchange current density of 2.0 × 10 -10 A cm -2, whereas an amorphous film deposited at 50 °C has a Tafel slope of 36 mV/decade and an exchange current density of 5.4 × 10 -12 A cm -2. Because the films deposited from refluxing electrolyte deposit directly as crystalline films, it is possible to deposit them epitaxially on single-crystal Au(100). This opens up the possibility to study the catalytic activity of different Co 3O 4 planes exposed to the electrolyte. © 2012 American Chemical Society.



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© 2012 American Chemical Society (ACS), All rights reserved.