Characterization and reactivity of oxygen-centred radicals over transition metal oxideclusters

Abstract

We introduce chemical structures and reactivity of oxygen-centred radicals (O⁻˙) over transition metal oxide (TMO) clusters based on mass spectrometric and density functional theory studies. Two main issues will be discussed: (1) the compositions of TMO clusters that have the bonding characteristics of (or contain) the O⁻˙ radicals; and (2) the dependences (cluster structures, sizes, charge states, metal types, etc.) of the chemical reactivity and selectivity for the O⁻˙ radicals over TMO clusters. One of the goals of cluster chemistry is to understand the elementary reactions involved with complex heterogeneous catalysis. The study of the O⁻˙ containing TMO clusters permits rather detailed descriptions for how mono-nuclear oxygen-centred radicals may exist and react with small molecules over TMO based catalysts.