Strong Metal–Support Interactions Enhance the Pairwise Selectivity of Parahydrogen Addition over Ir/TiO₂

The effects of strong metal–support interactions (SMSI) on the pairwise selectivity of propene hydrogenation over metal-oxide-supported Ir nanoparticles were investigated using parahydrogen-enhanced NMR spectroscopy. A ∼20-fold increase in the pairwise selectivity was observed following a reduction treatment of the Ir/TiO 2 catalyst at 500 °C. Consistent with SMSI, the effects could be completely reversed by oxidation followed by rereduction at 200 °C. Noninteracting supports, such as Al 2 O 3 and SiO 2, did not show this behavior. X-ray photoelectron spectroscopy reveals partial reduction of the TiO 2 support, and STEM data reveal flattening of Ir particles after high-temperature reduction. The presence of chloride ions during activation was found to further promote pairwise selectivity but only for the Ir/TiO 2 catalyst. The results are interpreted in terms of the electronic and possible geometric blocking effects associated with SMSI.