Facet-Dependent Selectivity of Rutile IrO₂ for Oxygen and Chlorine Evolution Reactions

Water electrolysis is a promising route for sustainable production of hydrogen as an energy storage medium and valuable precursor for industrial chemical syntheses such as ammonia and methanol. Direct electrolysis of seawater circumvents costly desalination and purification steps to reduce the price of renewable hydrogen to achieve cost parity with carbon-intensive steam reforming. However, the significant concentration of chloride salts in seawater poses a challenge to selectivity of seawater electrolysis. In aqueous chloride electrolytes, the chlorine evolution reaction (CER) is kinetically favored over the oxygen evolution reaction (OER). Rutile-type iridium dioxide (IrO 2 ) is a state-of-the-art electrocatalyst for water electrolysis but is also a benchmark chlorine evolution electrocatalyst in the industrial chlor-alkali process. Understanding OER/CER selectivity is needed to make seawater electrolysis a viable energy conversion technology in the future. In this work, we seek to understand the relationship between crystallographic facet and competitive reaction pathway between OER and CER on epitaxial, rutile IrO 2 thin films. We investigate facet-dependent OER and CER activity on a series of single-crystalline IrO 2 thin films using a rotating disk electrode geometry. The OER/CER selectivity, reaction rate order, and reaction intermediate electroadsorption affinities are explored to add fundamental insight into the reactivity of rutile IrO 2 surface. To gain further insight into OER intermediate adsorption affinities, we paired electrochemical measurements with surface-sensitive ambient pressure x-ray photoelectron spectroscopy (AP-XPS). Moving forward, our facet-dependent study of OER/CER selectivity of rutile IrO 2 can be used to design selective seawater electrocatalysts for cost-effective and sustainable hydrogen production.