Fe"' tetraphenylporphyrin chloride (FeCITPP) has been pyrolysed at different temperatures (450-850 "C) for different lengths of time (10-260 min). Some of the samples were mixed with carbon black in a 50/50 (w/w) proportion. Mossbauer spectra were obtained for these catalyst powders. The spectra reveal a number of different sites, occurring with different relative abundance depending on the pretreatment. XPS and electrochemical measurements have also been performed using the same samples. The electrocatalytic properties can be described as a function of the abundance of the various sites and the XPS data were used to support the interpretation.

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The Hartree-Fock method is used to calculate the values of 1 'l'(0) I' for a number of configurations of different Fe ions. An interpolation formula for 1 'l'(0) I' as a function of the occupation number of valence electron orbitals (3d, 4s, 4p) is given. Experimental Mossbauer isomer shifts are correlated to estimated configurations which are compared to available MO calculations for a few cases.

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