Evolution of structure and chemistry of bimetallic nanoparticle catalysts under reaction conditions.

Three series of bimetallic nanoparticle catalysts (Rh(x)Pd(1-x), Rh(x)Pt(1-x), and Pd(x)Pt(1-x), x = 0.2, 0.5, 0.8) were synthesized using one-step colloidal chemistry. X-ray photoelectron spectroscopy (XPS) depth profiles using different X-ray energies and scanning transmission electron microscopy showed that the as-synthesized Rh(x)Pd(1-x) and Pd(x)Pt(1-x) nanoparticles have a core-shell structure whereas the Rh(x)Pt(1-x) alloys are more homogeneous in structure. The evolution of their structures and chemistry under oxidizing and reducing conditions was studied with ambient-pressure XPS (AP-XPS) in the Torr pressure range. The Rh(x)Pd(1-x) and Rh(x)Pt(1-x) nanoparticles undergo reversible changes of surface composition and chemical state when the reactant gases change from oxidizing (NO or O(2) at 300 degrees C) to reducing (H(2) or CO at 300 degrees C) or catalytic (mixture of NO and CO at 300 degrees C). In contrast, no significant change in the distribution of the Pd and Pt atoms in the Pd(x)Pt(1-x) nanoparticles was observed. The difference in restructuring behavior under these reaction conditions in the three series of bimetallic nanoparticle catalysts is correlated with the surface free energy of the metals and the heat of formation of the metallic oxides. The observation of structural evolution of bimetallic nanoparticles under different reaction conditions suggests the importance of in situ studies of surface structures of nanoparticle catalysts.

Reaction-driven restructuring of Rh-Pd and Pt-Pd core-shell nanoparticles.

Heterogeneous catalysts that contain bimetallic nanoparticles may undergo segregation of the metals, driven by oxidizing and reducing environments. The structure and composition of core-shell Rh(0.5)Pd(0.5) and Pt(0.5)Pd(0.5) nanoparticle catalysts were studied in situ, during oxidizing, reducing, and catalytic reactions involving NO, O2, CO, and H2 by x-ray photoelectron spectroscopy at near-ambient pressure. The Rh(0.5)Pd(0.5) nanoparticles underwent dramatic and reversible changes in composition and chemical state in response to oxidizing or reducing conditions. In contrast, no substantial segregation of Pd or Pt atoms was found in Pt(0.5)Pd(0.5) nanoparticles. The different behaviors in restructuring and chemical response of Rh(0.5)Pd(0.5) and Pt(0.5)Pd(0.5) nanoparticle catalysts under the same reaction conditions illustrates the flexibility and tunability of the structure of bimetallic nanoparticle catalysts during catalytic reactions.