Abstract
This paper reports on an EPR and catalytic study of a novel [Fe-porphyrin] catalyst, [FeR4P], used for the catalytic decomposition of pentacholorophenol (PCP). The porphyrin complex [FeR4P] bears 2,6-di-tert-butylphenols (where R = di-ButPhen) at each meso-aryl position of the porphyrin ring. The FeR4P-SiO2 catalyst was found to be very efficient for the degradation of PCP, using NaIO4 as oxidant plus imidazole as cocatalyst. EPR spectroscopy shows that in the presence of the oxidant NaIO4, at a redox potential of Eh = 250 mV, [FeR4P] forms a high valent [FeIV = O Por+· ] state with an EPR spectrum characterized by effective g-values g ⊥ eff = 3.41 and g || eff = 2, similar to Compound I of Horseradish Peroxidase. The [FeIV = O Por+· ] state can described by a S = 1 state of the oxoferryl FeIV = O weakly coupled by exchange interaction J to a S′ = 1/2 porphyrin cation radical. The zero field splitting of the FeIV = O is D = +16.5 K and the coupling parameters are J/D = 0.31, J = +5.2 K. We suggest that the formation of [FeIV = O Por+· ] specie to be the key intermediate responsible for the observed efficient catalytic decomposition of PCP.
Acknowledgement
This work has been supported by a Greek-Russia bilateral collaboration project funded by the General Secretariat for Research and Technology (GGET).