Increasing Iridium Oxide Activity for the Oxygen Evolution Reaction with Hafnium Modification.

Synthesis and implementation of highly active, stable, and affordable electrocatalysts for the oxygen evolution reaction (OER) is a major challenge in developing energy efficient and economically viable energy conversion devices such as electrolyzers, rechargeable metal-air batteries, and regenerative fuel cells. The current benchmark electrocatalyst for OER is based on iridium oxide (IrO) due to its superior performance and excellent stability. However, large scale applications using IrO are impractical due to its low abundance and high cost. Herein, we report a highly active hafnium-modified iridium oxide (IrHfO) electrocatalyst for OER. The IrHfO electrocatalyst demonstrated ten times higher activity in alkaline conditions (pH = 11) and four times higher activity in acid conditions (pH = 1) than a IrO electrocatalyst. The highest intrinsic mass activity of the IrHfO catalyst in acid conditions was calculated as 6950 A g at an overpotential (η) of 0.3 V. Combined studies utilizing operando surface enhanced Raman spectroscopy (SERS) and DFT calculations revealed that the active sites for OER are the Ir-O species for both IrO and IrHfO catalysts. The presence of Hf sites leads to more negative charge states on nearby O sites, shortening of the bond lengths of Ir-O, and lowers free energies for OER intermediates that accelerate the OER process.