Unusual non-bulk properties in nanoscale materials: thermal metal-metal bond contraction of gamma-alumina-supported Pt catalysts.

Variable-temperature X-ray absorption spectroscopy measurements of sub-nanometer Pt nanoparticles on a high-surface-area gamma-alumina support reveal that the Pt-Pt bonds exhibit contraction upon heating [i.e., negative thermal expansion (NTE)]. Bare clusters under a He environment show an average linear expansion coefficient of -2.5 x 10-5 K-1 over the temperature range studied. Adsorption of hydrogen results in an overall bond relaxation and less dramatic Pt-Pt thermal bond-length contraction. From the temperature effect on bond length, disorder parameters, and the X-ray absorption near edge structure (XANES) spectra, temperature-dependent charge transfer between the support and the Pt clusters was concluded to be responsible for the observed behavior.