Formation and Segregation of the Ru- and Rh-MgO Solid Solutions.

Structural changes in Ru- and Rh-loaded magnesium oxide (MgO) subjected to thermal treatment were investigated by using X-ray absorption spectroscopy. The thermal treatment of the MgO-loaded Ru and Rh nanoparticles led to the formation of Ru-MgO and Rh-MgO solid solutions, respectively. The valences of Ru and Rh in the solutions were 4+ and 3+, respectively, as determined by the Ru and Rh K-edge X-ray absorption near-edge structure (XANES). The degree of solid solution formation was the highest at 873 and 1073 K in Ru-MgO and Rh-MgO, respectively, as observed in the extended X-ray absorption fine structure and XANES analyses. The nearest neighboring Ru-O and Rh-O bond distances were shorter than the Mg-O bond in MgO. The dispersion of Ru and Rh on the MgO surface, measured by CO adsorption, increased for samples thermally heated at 1273 K, suggesting that the segregation of Ru or Rh from the solid solutions occurred at this temperature. Consequently, a relatively high dispersion was realized in the sample thermally heated to 1273 K. A good correlation was found between the dispersion value of Ru in Ru/MgO and the NH decomposition activity.