TY - JOUR
T1 - Effect of oxygen electronic polarisability on catalytic reactions over oxides
AU - Idriss, H.
AU - Seebauer, E. G.
N1 - EGS acknowledges support of the US DOE (DEFG02-91ER45439) through the Materials Research Laboratory at UIUC. The authors gratefully acknowledge helpful discussions with Professor R.I. Masel.
PY - 2000/6
Y1 - 2000/6
N2 - This work examines two partial oxidation reactions over oxides (alcohols dehydrogenation to aldehydes and aldehydes esterification to esters) to determine how reaction rates can be quantitatively correlated with physical properties of the bulk catalysts. We show that while electronegativity difference, Δχ, metal-oxygen bond strength, EM-O. fail utterly, oxygen partial charge, qO, and oxygen Madelung potential, VMad(O), do provide limited correlations for the set of roughly twelve oxides examined. However, oxygen electronic polarisability, αO, does a much better job. We rationalise this finding in terms of the concept of chemical hardness in what appears to be the first successful application of this idea to oxide reactivity.
AB - This work examines two partial oxidation reactions over oxides (alcohols dehydrogenation to aldehydes and aldehydes esterification to esters) to determine how reaction rates can be quantitatively correlated with physical properties of the bulk catalysts. We show that while electronegativity difference, Δχ, metal-oxygen bond strength, EM-O. fail utterly, oxygen partial charge, qO, and oxygen Madelung potential, VMad(O), do provide limited correlations for the set of roughly twelve oxides examined. However, oxygen electronic polarisability, αO, does a much better job. We rationalise this finding in terms of the concept of chemical hardness in what appears to be the first successful application of this idea to oxide reactivity.
KW - Electronegativity difference
KW - Ethanol dehydrogenation oxides
KW - Madelung potential oxides
KW - Oxygen polarisability
KW - Tishchenko reaction oxides
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U2 - 10.1023/A:1019055824776
DO - 10.1023/A:1019055824776
M3 - Article
AN - SCOPUS:0034210302
SN - 1011-372X
VL - 66
SP - 139
EP - 145
JO - Catalysis Letters
JF - Catalysis Letters
IS - 3
ER -