We present detailed results of a multiple-scattering (MS) extended x-ray absorption fine structure (EXAFS) data analysis of crystalline and nanocrystalline platinum. Advanced MS EXAFS analysis has been applied to raw x-ray absorption data including the background, using the expansion of the absorption cross section in terms of local two-body and three-body configurations. Present EXAFS results on bulk Pt are found to be in agreement with previous structural and vibrational data, and has been used as a reference for reliable structural refinement of nanosized systems. EXAFS structural refinement of Pt nanoparticles has been performed in combination with electron microscopy and x-ray diffraction, showing the importance of considering the actual size distribution and morphology of the samples. Present samples were unsupported and supported Pt nanocrystalline systems with size distributions showing clusters of quasispherical shape in the $1–7\mathrm{nm}$ range. In particular, EXAFS spectra have been analyzed accounting for the reduction of the coordination number and degeneracy of three-body configurations, resulting from the measured size distribution and expected surface atom contributions. The importance of a correct account of the reduction of the number of neighbors for calculating MS contributions is emphasized in the paper. EXAFS results have been found compatible with x-ray diffraction and transmission electron microscopy investigations. We estimate that EXAFS could be used to study cluster shapes only for sizes below $2\mathrm{nm}$ using present methods and quality of the experimental data. We have also shown that the local distribution of distances and angles probed by EXAFS is broader than in bulk Pt, with first-neighbor bond length variance and asymmetry increasing upon reducing the particle size. Methods and results presented in this paper have been found to be successful for a robust structural refinement of monatomic nanocrystalline systems and represents a solid starting point for analyzing subtle structural and dynamical local changes occurring during in situ experiments involving nanomaterials for specific applications like supported nanocatalysts.

The evolution of the solid electrolyte interface (SEI) in carbon-coated ZnFe₂O₄ (ZFO-C) anodes is studied by soft X-ray absorption spectroscopy (XAS). Experiments probe locally the SEI growth in the 2–100 nm range, using both total electron (TEY) and total fluorescence (TFY) yield techniques. XAS analysis shows that the SEI grows preferentially around the ZFO-C nanoparticles.

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm⁻²) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalystPt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XASin situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5–2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.