Electronic and Compositional Modulation of SMSI States for Selective CO2 Hydrogenation with Rhodium Catalysts

High Resolution Image Download MS PowerPoint Slide The role of TiO 2, ZnO, and ZnTiO 3 as supports for rhodium has been investigated for the CO 2 hydrogenation. Rh/TiO 2 demonstrated a high selectivity for CH 4, which is typical for Rh catalysts; however, Rh/ZnO and Rh/ZnTiO 3 shifted the product selectivity to CO almost exclusively. The difference in behavior is attributed to the modulation of strong metal–support interactions (SMSIs) by the supports. Detailed characterization revealed the formation of a distinct metallic Zn overlayer covering the RhZn x alloyed nanoparticle in Rh/ZnO, altering the electronic states of Rh, and a RhTi x overlayer in Rh/ZnTiO 3, suppressing the CO adsorption on Rh in bridged and tilted geometry and polarizing the CO bond. These structural features significantly modify the CO adsorption strength and mode, together with the intermediate hydrogenation behavi…