Application of a Novel Differential XAFS Approach for Determination of Coordination Geometries

A novel differential XAFS approach has been developed which allows the determination of small distortions in coordination geometry (distortions in bond lengths and angles) about the absorber. The approach requires taking the difference, Δχ, between the XAFS of the sample and a reference material. The Fourier transform of Δχ directly reveals the average of the altered path lengths between the sample and the reference. More importantly, the amplitude of Δχ directly reflects the magnitude of the changes in the bond lengths or angles. FEFF6 calculations verify this approach, and help to interpret the data. Application of this technique has been made to the zincate ion in an alkaline Zn battery, where small distortions from the Td geometry resulting from ion pair interactions can be determined directly

A New Model Describing the Metal-Support Interaction in Noble Metal Catalysts

The catalytic activity and spectroscopic properties of supported noble metal catalysts are strongly influenced by the acidity/alkalinity of the support but are relatively independent of the metal (Pd or Pt) or the type of support (zeolite LTL or SiO{2}). As the alkalinity of the support increases, the TOF of the metal particles for neopentane hydrogenolysis decreases. At the same time, there is a decrease in the XPS binding energy and a shift from linear to bridge bonded CO in the IR spectra. Analysis of the shape resonance in XANES spectra indicates that in the presence of chemisorbed hydrogen the difference in energy between the Pt-H antibonding orbital and the Fermi level decreases as the alkalinity of the support increases. Based on the results from the IR, XPS, and shape resonance data a new model is proposed in which the interaction between the metal and support leads to a shift in the energy of the metal valence orbitals. The EXAFS structural analysis indicates that the small metal particles are in contact only with the oxide ions of the support. Finally, a new spectroscopic characterisation, Atomic XAFS, is presented which provides new insights into the origin of the electronic changes in the metal. As the alkalinity of the support increases, there is decrease in the metal ionisation potential. The primary interaction is a Coulomb attraction between metal particle and support oxygen ions, which affects the metal interatomic potential. This model for the metal-support interaction explicitly excludes the need for electron transfer, and it can account for all observed changes in the catalytic, electronic, and structural properties of the supported metal particles induced by support acidity ranging from acidic to neutral to alkaline