Atmosphere-Induced Transient Structural Transformations of Pd-Cu and Pt-Cu Alloy Nanocrystals

We have investigated the transformations of colloidal Pd-Cu and Pt-Cu bimetallic alloy nanocrystals (NCs) supported on γ-Al₂O₃ when exposed to a sequence of oxidizing and then reducing atmospheres, in both cases at high temperature (350 °C). A combination of in situ diffuse reflectance infrared Fourier transform spectroscopy and X-ray absorption spectroscopy was employed to probe the NC surface chemistry and structural/compositional variations in response to the different test conditions. Depending on the type of noble metal in the bimetallic NCs (whether Pd or Pt), different outcomes were observed. The oxidizing treatment on Pd-Cu NCs led to the formation of a PdCuO mixed oxide and PdO along with a minor fraction of CuO _x species on the support. The same treatment on Pt-Cu NCs caused a complete dealloying between Pt and Cu, forming separate Pt NCs with a minor fraction of PtO NCs and CuO _x species, the latter finely dispersed on the support. The reducing treatment that followed the oxidizing treatment largely restored the Pd-Cu alloy NCs, although with a residual fraction of CuO _x species remaining. Similarly, Pt-Cu NCs were partially restored but with a large fraction of CuO _x species still located on the support. Our results indicate that the noble metal present in the bimetallic Cu-based alloy NCs has a strong influence on the dealloying/migrations/realloying processes occurring under typical heterogeneous catalytic reactions, elucidating the structural/compositional variations of these NCs depending on the atmospheres to which they are exposed.