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Reinterpreting volcano correlations in bio-inspired Electrocatalysts: The role of active site availability in oxygen reduction
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DOI：10.1016/j.elecom.2026.108157.png)
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Abstract
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The binding energy EM- O2 of dioxygen to active sites is the most common reactivity descriptor for the electroreduction of O2 promoted by metals and for macrocyclic MN4 molecular catalysts. When activity is plotted as log(j)E versus the M - O2 binding energy, a volcano-shaped correlation is obtained with perfluorinated iron phthalocyanine (16(F)FePc), showing the highest activity. However, we report here that, surprisingly, in spite of its high activity, 16(F)FePc exhibits the largest activation energy of a series of MN4 complexes examined. In contrast, biomimetic Fe porphyrins appear on the low activity section of the descending region of the volcano plot and exhibit very low and even negative activation energies. The apparent low activity of Fe porphyrins as log(j)Eis attributed to the extremely low concentration of Fe(II) active sites at the potential E chosen for comparing the activity in a volcano plot. In alkaline media, under those conditions Fe porphyrins predominate in the inactive state Fe(III)-OH state. Fe porphyrins exhibit strong O2 binding energies that probably facilitate fast electron transfer to the bound O2, as in aerobic life. Thus, the descending region of the volcano can be understood in terms of a new Principle, stated as follows For an electrocatalytic process to proceed at an optimal rate, the applied overpotential must not be high enough to drive sufficient current, but low enough to avoid converting the metal center to an inactive oxidation state.
Keywords:
Oxygen reduction reaction
Volcano correlation
Activation energies
Sabatier principle
Zagal principle
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