Proceedings of September Meeting 2016 (NFM16)
Publication date: 14th June 2016
The oxidation of water provides the electrons to reduce protons or carbon dioxide to a fuel hence it is expected to play a major role in the development of energy conversion and storage technologies. However, the slow rate of the water oxidation (the oxygen evolution reaction – OER) remains a main challenge and requires design of highly active and stable electrocatalysts. Here we show a study of IrNi@IrOx metal-oxide core-shell nanoparticles with significantly enhanced intrinsic activity compared to pure Ir@IrOx nanoparticles - one of the most active and stable electrocatalysts for water oxidation. We probed the Ir sites in Ir@IrOx and IrNi@IrOx in operando condition using X-ray absorption near edge structure and extended X-ray absorption fine structure. Ir-O bond distance in IrNi@IrOx were significantly shortened compared to in Ir@IrOx. Correlating the structure with the OER activity, we demonstrate that the electronic and geometric structure of the metal center and the electrophilicity of oxygen ions play an essential role in OER activity of the electrocatalyst. This finding paves a way to the molecular machinery of highly active electrocatalysts for water oxidation.
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