Interrogating site dependent kinetics over SiO₂-supported Pt nanoparticles

A detailed knowledge of reaction kinetics is key to the development of new more efficient heterogeneous catalytic processes. However, the ability to resolve site dependent kinetics has been largely limited to surface science experiments on model systems. Herein, we can bypass the pressure, materials, and temperature gaps, resolving and quantifying two distinct pathways for CO oxidation over SiO₂-supported 2 nm Pt nanoparticles using transient pressure pulse experiments. We find that the pathway distribution directly correlates with the distribution of well-coordinated (e.g., terrace) and under-coordinated (e.g., edge, vertex) CO adsorption sites on the 2 nm Pt nanoparticles as measured by in situ DRIFTS. We conclude that well-coordinated sites follow classic Langmuir-Hinshelwood kinetics, but under-coordinated sites follow non-standard kinetics with CO oxidation being barrierless but conversely also slow. This fundamental method of kinetic site deconvolution is broadly applicable to other catalytic systems, affording bridging of the complexity gap in heterogeneous catalysis.