Formation and Segregation of a Pd-MgO Solid Solution Studied by X-ray Absorption Spectroscopy.

Thermal treatment of Pd nanoparticles or Pd(NH)(NO) supported on MgO resulted in the formation of a solid solution of Pd-MgO, as evidenced by Pd K-edge X-ray absorption fine structure (XAFS). The valence of Pd in the Pd-MgO solid solution was determined to be 4+ from the comparison of X-ray absorption near edge structure (XANES) with reference compounds. A characteristic shrinkage of the Pd-O bond distance was observed in comparison with that of the nearest-neighboring Mg-O bond in MgO, which agreed with the density functional theory (DFT) calculations. The two-spike pattern was observed in the dispersion of Pd-MgO owing to the formation and successive segregation of solid solutions above 1073 K.