Study of Supported PtCu and PdAu Bimetallic Nanoparticles Using In-Situ X-ray Tools

A combination of two synchrotron X-ray techniques, X-ray absorption spectroscopy (XAS), and pair distribution function analysis (PDF) with complementary Fourier transform infrared (FTIR) spectroscopy measurement, was used to characterize the composition distributions of PdAu and PtCu bimetallic particles after treatment in H2 or CO and in the presence of these gases. This is the first reported application of PDF to the study of supported bimetallic nanoparticles. We found that XAS was informative in determining the component distribution of an initial sample, but PDF was better suited to following changes in the distribution upon changing the gas environment. Thus, the surface of a PtCu bimetallic particle of about 2.5 nm after treatment in H2 was found to be enriched in Cu, while the core was bimetallic. There was no evidence of a component-segregated core−shell structure. Treatment in CO caused enrichment of Pt to the surface layer, with a concomitant migration of Cu to the core. The average particle size remained the same. For the PdAu bimetallic particles, the surface and core compositions were similar after H2 treatment, and Pd was enriched in the surface after CO treatment. The X-ray results compared favorably to infrared spectroscopy results. The results demonstrated that the two X-ray techniques in combination can generate new information not available with either technique alone or other techniques, about the elemental distribution of bimetallic particles under conditions relevant to catalysis. They could provide new insight into structure−function relationships and time-on-stream behavior of bimetallic catalysts.