(461f) Scaling Approaches to Solvent-Adsorbate Interactions

Increased efforts have been devoted to understanding fundamentals of the interface between heterogeneous metal catalysts and a condensed phase.¹ However, the effective use of static electronic structure calculations (e.g. DFT) at the interface remains challenging due to the vast configurational space associated with the ordering of the free solvent. This becomes particularly burdensome when attempting to study detailed reaction mechanisms and/or perform catalyst screening studies, motivating the development of more efficient approaches to modeling the interfacial environment.^2-3

In this presentation, we discuss the presence of energy scaling relationships, which have been instrumental in the discovery of improved catalysts in gas-phase reaction contexts,⁴ in the context of microsolvation environments. We show how the nature of energy scaling changes (or doesn’t) in the presence of one, two, or several molecules of varying solvents (e.g. water, methanol, acetonitrile), thereby offering insights into how energy scaling may affect reactivity toward the limit of a full solvation environment. The presence of the microsolvation environment has differential effects on the adsorption energies of different surface-bound molecules that depend on the nature of the adsorbate, thus offering a possible lever to tune reactivity and “break scaling” using solvent identity.

¹Saleheen, M. and Heyden, A. ACS Catal. 8, 2188 (2018).
²Bodenschatz, C., Sarupria, S., and Getman, R. B., J. Phys. Chem. C 119, 13642 (2016).
³Calle-Vallejo, F., de Morais, R. F., Illas, F., Loffreda, D., and Sautet, P., J. Phys. Chem. C 123, 5578 (2019).
⁴Nørskov, J.K., Bligaard, T., Rossmeisl, J., and Christensen, C. H., Nature Chem. 1, 37 (2009).