Element-ratio dependence of the 5d-states of Au and Pt in solid-solution-type Au-Pt alloy nanoparticles studied by X-ray absorption spectroscopy and density functional theory

Solid-solution-type Au-Pt alloy nanoparticles (NPs) were prepared from the nanoclusters of each metal using the polymer-conjugated fusion growth method. The elemental mapping analysis showed that the mixing state of the elements in the NPs drastically changed in the narrow reaction-temperature range from 100 degrees C to 180 degrees C. For their various mixing states, the 5d-states of Au and Pt atoms in the alloy NPs were investigated on the basis of the white line intensities of X-ray absorption near edge structure (XANES). Then, the 5d-states of Au and Pt atoms in a model crystalline ordered alloy structures were investigated on the basis of the theoretically calculated XANES spectra using density functional theory (DFT) in the whole composition range. The DFT calculation showed that the changes in the absorption spectra near the Pt and Au edges are caused by the change in the occupation of the Pt 5d-states and the orbital hybridisation of the Au 5d-states with the 5d-states of neighbouring Pt atoms around an Au atom, respectively. The study revealed element-ratio dependence of the 5d-states and mechanism of the 5d-state changes in solid-solution-type Au-Pt alloy nanoparticles.