5 years ago

Factors Determining the Rate and Selectivity of 4e–/4H+ Electrocatalytic Reduction of Dioxygen by Iron Porphyrin Complexes

Factors Determining the Rate and Selectivity of 4e–/4H+ Electrocatalytic Reduction of Dioxygen by Iron Porphyrin Complexes
Biswajit Mondal, Subal Dey, Kushal Sengupta, Sudipta Chatterjee, Abhishek Dey
Reactivity as well as selectivity are crucial in the activation and electrocatalytic reduction of molecular oxygen. Recent developments in the understanding of the mechanism of electrocatalytic O2 reduction by iron porphyrin complexes in situ using surface enhanced resonance Raman spectroscopy coupled to rotating disc electrochemistry (SERRS-RDE) in conjunction with H/D isotope effects on electrocatalytic current reveals that the rate of O2 reduction, ∼104 to 105 M–1 s–1 for simple iron porphyrins, is limited by the rate of O–O bond cleavage of an intermediate ferric peroxide species (FeIII–OOH). SERRS-RDE probes the system in operando when it is under steady state such that any intermediate species that has a greater rate of formation relative to its rate of decay, including the rate determining species, would accumulate and can be identified. This technique is particularly well suited to investigate iron porphyrin electrocatalysts as the intense symmetric ligand vibrations allow determination of the oxidation and spin states of the bound iron with high fidelity.

Publisher URL: http://dx.doi.org/10.1021/acs.accounts.7b00192

DOI: 10.1021/acs.accounts.7b00192

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