Journal
JOURNAL OF SOLID STATE ELECTROCHEMISTRY
Volume 7, Issue 9, Pages 626-631Publisher
SPRINGER-VERLAG
DOI: 10.1007/s10008-003-0437-1
Keywords
hydrazine oxidation; iron phthalocyanines; electrocatalysis; volcano plots; Hammett parameters
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The activity of the different iron phthalocyanines was examined using the complexes adsorbed on graphite electrodes. The effect of the Fe(II)/(I) formal potential of iron phthalocyanines on the their catalytic activity for the electro-oxidation of hydrazine was investigated. A plot of log k (rate constant at constant potential) versus the Fe(II)/(I) formal potential gives a volcano curve. The rate of the reaction increases with the driving force of the catalyst (measured as its formal potential) and then decreases for higher driving forces. A similar graph is obtained with a plot of log k versus the sum of the Hammett parameters of the substituents on the periphery of the phthalocyanine ligand. A maximum activity is obtained for a complexes having an M(II)/(I) redox potential close to -0.6 V which agrees with previous studies conducted with phthalocyanines of different metals and with cobalt phthalocyanines bearing different substituents.
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