Heterogeneous Catalysis and Beyond: A First-Principles Multiscale Modeling Perspective

First-principles electronic structure calculations have emerged as a key contributor in modern heterogeneous catalysis research. Next to the dedicated computation of thermostability, spectroscopic signals and reactivity descriptors, they are increasingly used as basis for predictive-quality multiscale modeling approaches. Corresponding approaches additionally account for meso- and macroscopic aspects like statistical interplay or heat and mass transport. This provides unprecedented insight into the catalytic function, be that the actual reaction mechanism or the nature of the surface of the operating catalyst.
In the first part of the talk I will illustrate this within the context of model catalyst studies at ambient conditions. Specifically addressing recent in situ experiments on CO oxidation at Pd(100) I will demonstrate how multi-scale modeling can be employed to conclude not only on the phases predominantly present at the surface in the measurements, but also to discriminate which of these predominantly actuate the catalysis. Using this methodological framework as a basis, the second part of the talk will then discuss the multiple challenges to theory imposed by various forms of driven catalysis. In contrast to unspecific thermal excitation, these forms of catalysis aim to accelerate surface chemical transformations by selectively pumping and storing energy into defined degrees of freedom. Theory needs to additionally account for the employed fields, photons or bias, often at solid-liquid interfaces an endeavor that has only just begun.