Two Distinct Oxidation Dispersion Mechanisms in Pd-CeO2 Mediated by Thermodynamic and Kinetic Behaviors of Single Pd Species

TL;DR

This study reveals two distinct oxidation dispersion mechanisms in Pd-CeO2 catalysts driven by temperature-dependent thermodynamic and kinetic behaviors of single Pd species, providing insights for precise catalyst control.

Contribution

The paper uncovers the atomic-level dispersion mechanisms of Pd on CeO2, highlighting the roles of thermodynamics and kinetics in different temperature regimes, using advanced microscopy and calculations.

Findings

At lower temperatures, Pd undergoes oxidation and limited dispersion.

At higher temperatures, Pd remains metallic and disperses directly.

Different dispersion pathways are driven by environment-dependent Pd species behaviors.

Abstract

Understanding the dispersion process of supported catalysts is crucial for synthesizing atomic-level dispersed catalysts and precisely manipulating their chemical state. However, the underlying dispersion mechanism remains elusive due to the lack of atomic-level evidence during the dispersion process. Herein, by employing spherical aberration-corrected environmental scanning transmission electron microscopy (ESTEM), first-principles calculations, and a global optimization algorithm, we unraveled the pre-oxidation dispersion and direct dispersion mechanisms in the Pd/CeO2 (100) system, mediated by the thermodynamic and kinetic behaviors of single Pd species. We discovered that at lower temperatures, the Pd nanoparticles first undergo oxidation followed by the dispersion of PdO, while at higher temperatures, the entire dispersion process of Pd remains in a metallic state. The distinct dispersion mechanisms at different temperatures are driven by the thermodynamic and kinetic differences of environment-dependent single Pd species. The nonmobile Pd1O4 species stabilized at lower temperatures obstructs the direct dispersion of Pd nanoparticles, instead triggering a sequence of pre-oxidation followed by limited dispersion. In contrast, the highly mobile Pd1O2 species at higher temperatures facilitates the complete and direct dispersion of Pd nanoparticles. This research illuminates the essential physical mechanisms of oxidative dispersion from both thermodynamic and kinetic perspectives, potentially enabling strategies for precisely controlling the state of highly dispersed catalysts.