Two π-extended cobalt porphyrins are synthesized and one of them is crystallographically characterized. The nanocomposites of nonplanar () porphyrin immobilized multi-walled carbon nanotubes were thoroughly characterized spectroscopically and microscopically, showing ∼200 mV positive shift in the O reduction peak potential in aqueous media and ∼100 mV shift in the onset potential of the O reduction relative to the control -tetraphenylporphyrinatocobalt(II) nanocomposite. Both the π-extended cobalt porphyrin immobilized nanocomposites efficiently catalyze selective 4e/4H O reduction under ambient conditions with excellent methanol tolerance and high stability due to effective π-π interactions, and could be an alternative for expensive Pt-based cathode materials in fuel cells.
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