The utilization of metal alkoxides as single-source precursors for (mixed-)oxide materials offers remarkable benefits, such as the possibility to precisely control the metal ratio in the resulting material, highly homogeneous distribution of the elements in the film, and the low temperatures required for film processing. Herein we report on the isolation and characterization of the bimetallic Co-Mo alkoxide [Co3 Mo4 O10 (OCH3 )10 (dmf)4 ] (Co3 Mo4 ; dmf=N,N-dimethylformamide), which was prepared by the anion metathesis reaction of the corresponding metal chlorides. The Co-Mo alkoxide was explored as a well-defined precursor of cobalt oxide catalysts for the oxygen evolution reaction (OER) in alkaline electrolyte MOH. The catalysts demonstrated excellent activity in the OER, manifested in low onset potentials and Tafel slopes and superb stability under the operating conditions both in alkaline and nearly neutral media. It was observed that the nature of the metal cation of the alkaline electrolyte MOH (M+ =Li+ , Na+ , K+ , Cs+ ) greatly affected the catalytic performance of the material. We propose that the positive effect of larger metal cations on the film activity in the OER could be explained by the higher hydration enthalpies of larger ions and enhanced mass transport within a larger interlayer space between the [CoO2 ]δ-∞ sheets of the in situ formed binary oxides. It may be deduced that this trend is universal and may be extended to other types of metal oxides forming layered structures during the OER.
Keywords: alkoxides; cobalt; molybdenum; oxygen evolution reaction; single-source precursor chemistry; water splitting.
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