The dissociative chemisorption of formic acid, HCOOH, to surface formate species, HCOO-M, on metal oxide catalysts was examined. The chemisorption studies reveal an average of similar to5-6 mumol/m(2) of active surface sites for many of the metal oxide catalysts. From TPD experiments, the decomposition temperatures of the surface formate (T-p) were found to vary from 88 to 313degreesC. The turnover frequency (TOF) values for formic acid oxidation were found to vary over I I orders of magnitude (10(-3)-10(8) s(-1)) at 250degreesC. No correlations were found between (i) H-2-TPR onset temperatures and the enthalpies of formation of bulk metal oxides (-DeltaH(f)), (ii) TOFs and H-2-TPR onset temperatures, or (iii) TOFs and the isotopic dioxygen exchange rates with the metal oxide lattice oxygen. Weak inverse correlations were found for both TOFs and catalytic activities versus -DeltaH(f). A strong inverse relationship was found between the TOFs and the surface formate decomposition temperatures, supporting the assertion that the rate-determining step during formic acid oxidation is the decomposition of the surface formate intermediate.