Effect of oxygen electronic polarisability on catalytic reactions over oxides

This work examines two partial oxidation reactions over oxides (alcohols de hydrogenation to aldehydes and aldehydes esterification to esters) to deter mine how reaction rates can be quantitatively correlated with physical prop erties of the bulk catalysts. We show that while electronegativity differen ce, Delta chi, metal-oxygen bond strength, EM-O, fail utterly, oxygen parti al charge, q(O), and oxygen Madelung potential, V-Mad (O), do provide limit ed correlations for the set of roughly twelve oxides examined. However, oxy gen electronic polarisability, alpha(O), does a much better job. We rationa lise this finding in terms of the concept of chemical hardness in what appe ars to be the first successful application of this idea to oxide reactivity .