Surface chlorination of IrO2(110) by HCl

The ability to controllably chlorinate metal-oxide surfaces can provide opportunities for designing selective oxidation catalysts. In the present study, we investigated the surface chlorination of IrO2(110) by HCl using temperature programmed reaction spectroscopy (TPRS), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We find that exposing IrO2(110) to HCl, followed by heating to 650 K in ultrahigh vacuum, produces nearly equal quantities of on-top and bridging Cl atoms on the surface, Cl-t and Cl-br, where the Cl-br atoms replace O-atoms that are removed from the surface by H2O formation. After HCl adsorption at 85 K, only H2O desorbs at low Cl coverages during TPRS, but HCl begins to desorb in increasing yields as the Cl coverage is increased above about 0.5 monolayer (ML). The desorption of Cl-2 was not observed under any conditions, in good agreement with the high barrier for this reaction predicted by DFT. A maximum Cl coverage of 1 ML, with nearly equal coverages of Cl-t and Cl-br atoms, could be generated by reacting HCl with IrO2(110) in UHV. Our results suggest that a kinetic competition between recombinative HCl and H2O desorption under the conditions studied limits the saturation Cl coverage to a value less than the 2 ML maximum predicted by thermodynamics. XPS further shows that the partitioning of Cl between the Cl-t and Cl-br states can be altered by subjecting partially chlorinated IrO2(110) to reductive or oxidative treatments, demonstrating that the Cl site population can change dynamically in response to the gas environment. Our results provide insights for understanding the chlorination of IrO2(110) by HCl and can enable future experimental studies to determine how Cl-modification alters the surface chemical reactivity of IrO2(110) and potentially enhances selectivity toward partial oxidation chemistry.