Abstract
X-ray absorption spectra characterizing the metal-support interface in supported metal complexes and supported metal catalysts are summarized and evaluated. Single-metal-atom transition metal complexes on non-reducible metal oxide supports are bonded with metal-oxygen bonds with metal-oxygen distances of approximately 2.15 A; the bonding distance is only weakly sensitive to the oxidation state of the metal. Nearly this same metal-oxygen distance is characteristic of the metal-support interface in metal-oxide-supported metal clusters following high temperature reduction in H2 (HTR:T > 450 °C). The metals at the interface may be polarized sufficiently that they bond with the oxygen of the support much as the cations in mononuclear complexes bond with it. When the supported metals are treated in H2 at low temperatures (LTR:T < 350 °C) or are prepared under He with partially hydroxylated supports, a longer metal-support oxygen distance is observed, typically 2.5–2.7 A. This distance is suggested to characterize interactions between zero-valent metals and support oxygen. Changes in the performance of supported metal catalysts resulting from differences in the temperature of pretreatment in H2 are attributed to changes in the electronic properties and/or morphology of the metal clusters, which are suggested to be related to the concomitant changes in the structure of the metal-support interface.
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