Nickel hydroxide electrocatalysts for alcohol oxidation reactions: An evaluation by infrared spectroscopy and electrochemical methods

We have investigated the electrochemical oxidation of four alcohols (methanol, 1-, 2- and tertiary butanol) at Ni hydroxide electrodes in alkaline electrolytes. In situ FTIR spectroscopy and electrochemical methods have been used to examine these oxidation reactions. Oxidation of the primary and secondary alcohols commences in the potential region where it is proposed that multi-layers of NiOOH are formed on the electrode surface; while no reaction occurs with tertiary butanol. Methanol oxidation occurs in two stages, with predominantly formate being formed in the potential window 0.36-0.44 V (vs. SCE), followed by further oxidation to carbonate at potentials above approx. 0.45 V. Butanoate is the only detected reaction product for 1-butanol electrooxidation in the potential range 0.36-0.5 V. The oxidation of 2-butanol is more complex. In the lower potential range (0.36-0.44 V) the major reaction product is butanone, which is further oxidised at higher potentials to either acetate or a mixture of propanoate and formate (or carbonate). In addition, rate constants have been determined for the first stage of the electrochemical oxidation of all the alcohols investigated.