Paper SS+HC-MoA8
Elucidating Mechanisms of Alkanol Catalysis on SrTiO₃ Perovskite Surfaces using Density Functional Theory

Monday, October 22, 2018, 3:40 pm, Room 203C

Targeted at understanding observed differences in reaction dynamics for various alkyl alcohols on catalytic SrTiO₃ surfaces, we describe the results of our computational study of isopropanol adsorption and catalysis on SrTiO₃ (100). Using the PBE density functional with a Hubbard-U correction to initially probe the potential energy surface of adsorption, we have found a minimum-energy orientation for isopropanol adsorbed on the surface in good agreement with recent sum-frequency generation experiments. Continuing with this minimum, we followed multiple competing pathways and determined necessary transition states and intermediates in order to describe the kinetics and thermodynamics of these reactions. Armed with these results, we elucidate recent experimental findings favoring the formation of the dehydrogenation product acetone over the dehydration product propylene. Finally, we probed the adsorption potential energy surfaces of products in order to describe the contributions of product orientation and lateral surface diffusion to overall reaction dynamics. Our future work will consider different SrTiO₃ surfaces such as (111) and (110), as well as different alkanol adsorbates such as ethanol. Overall, these studies provide insight into the fundamental aspects of catalysis of this class of reagents on perovskite surfaces.