Tantalum Clusters Supported on Silica−Alumina: Influence of Support Composition and Chemistry on Cluster Structure

Abstract

Small cationic tantalum clusters were prepared on the surfaces of SiO₂, silica−aluminas, and γ-Al₂O₃ supports by treating physisorbed pentabenzyltantalum at 523 K for 24 h in flowing H₂. The rate of decomposition and the products formed in the decomposition of pentabenzyltantalum are dependent on the support composition. When the support was SiO₂, the evolved products were mainly biphenyl and a small amount of toluene, indicating that the Ta−C bond in pentabenzyltantalum was activated. As the alumina content of the support increased, diphenylmethane, benzene, and ethylene were increasingly formed, and these products show that the activation of the C−C bonds linking the C atoms of methyl groups to the aromatic rings of the benzyl ligands was facilitated. Infrared spectra of the surface species and mass spectra of the effluents formed during the treatment show that the composition of the support had significant influence on the decomposition of pentabenzyltantalum, and the chemistry is inferred to be related to the electron-donor properties of the supports. Extended X-ray absorption fine structure (EXAFS) spectra recorded at the Ta L_III edge indicate the formation of clusters with a Ta−Ta first-shell coordination number of ∼3, and images obtained by scanning transmission electron microscopy (STEM) confirm the presence of such small clusters. X-ray absorption near edge structure (XANES) data indicate that the formal oxidation state of the tantalum in the clusters decreased from ∼3.0 to ∼2.6 as the support was changed from SiO₂ to silica−aluminas to γ-Al₂O₃. The data suggest that the tantalum clusters were anchored to the supports via bridging O atoms. The EXAFS data show that the support composition had little influence on the cluster structure.