Model Approach in Heterogeneous Catalysis: Kinetics and Thermodynamics of Surface Reactions.

Heterogeneous catalysts are widely employed in technological applications, such as chemical manufacturing, energy harvesting, conversion and storage, and environmental technology. Often they consist of disperse metal nanoparticles anchored onto a morphologically complex oxide support. The compositional and structural complexity of such nanosized systems offers many degrees of freedom for tuning their catalytic performance. However, a rational design of heterogeneous catalysts based on an atomistic-level understanding of underlying surface processes has not been fully achieved so far and remains one of the primary goals for catalysis research. In our group, we developed concepts for replacing highly complex real supported catalysts by simplified model systems, which complexity can be gradually increased in order to mimic certain structural aspects of practically relevant catalysts in a controlled way. Well-defined model systems consisting of metal-nanoparticle ensembles supported on planar oxide substrates have proven to provide a successful approach to achieve fundamental insights into heterogeneous catalysis. In this Account, two mechanistic case studies focusing on an atomistic-level understanding of surface chemistry are presented in which we investigate how the nanoscopic nature of metal clusters affects their interaction with the adsorbates and the reactive processes. Particularly, we investigate the effects of the particle size and the flexibility of the atoms constituting metal clusters on the binding energy of gas-phase adsorbates, such as CO and oxygen. We identified two major structural factors determining the binding energy of gas phase adsorbates on metal nanoparticles: the local configuration of the adsorption site and the particle size. While the effect of the local configuration of the adsorption site was found to be adsorbate specific, the reduction of the cluster size results in a pronounced decrease of binding energy for both adsorbates and appears to be a general trend. In the second case study, we address the role of the surface modifiers, such as carbon, on the process of hydrogen diffusion into volume of Pd nanoparticles that was previously identified is an important step in hydrogenation chemistry. We provide for the first time direct experimental evidence that, inline with the recent theoretical predictions, the atomically flexible low-coordinated surface sites on Pd particles play a crucial role in the diffusion process and that their selective modification with carbon results in marked facilitation of subsurface hydrogen diffusion. By virtue of these examples, we demonstrate how model studies on complex nanostructured materials may provide an atomistic view of processes at the gas-solid interface related to heterogeneous catalysis.