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Heterogeneous catalysis of cyano-bridged polynuclear metal complexes, which were prepared by systematic replacement of C-bound metal ions (MC) and/or N-bound metal ions (MN) of Prussian blue ([MN(H2O)x]y[FeII/III(CN)6]; MN = FeIII, GaIII, MnII, ZnII or CoII: [FeII/III(H2O)x]y[MC(CN)6]; MC = FeII, PtIV, CoIII, IrIII or RuII), was examined for the hydrolysis of p-nitrophenol phosphate (p-NPP) as a model compound of insecticides. The catalytic activity of the complexes was enhanced by employing metal ions in higher oxidation states at the C- and N-bound sites, although only N-bound metal ions act as active sites. The dependence of the initial reaction rates for the hydrolysis on the initial concentration of p-NPP suggested that the rate determining step is the adsorption of p-NPP onto catalyst surfaces. The surface acidity of each complex estimated by the heat of pyridine desorption is strongly correlated with catalytic activity.

Effect of surface acidity of cyano-bridged polynuclear metal complexes on the catalytic activity for the hydrolysis of organophosphates