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Electrochemistry of metalloporphyrins and viologens at zeolite Y modified electrodes: evidence for electron trapping by monomolecular porphyrin layers

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100320a039· OSTI ID:6926025

Cyclic voltammetric data are presented for electrodes coated with zeolite Y powder containing porphyrins and viologens. Half-wave potentials for viologen cations (methylviologen, benzylviologen, or N,N'-(1,3-propenyl)-2,2'-bipyridinium) do not change significantly when they are exchanged into zeolite Y, whereas the reduction potentials for cobalt and zinc tetrakis(N-methyl-4-pyridyl)porphyrins shift (relative to aqueous solution) by + 200 mV. When a viologen cation is ion exchanged into the bulk of the zeolite, and cobalt tetrakis(N-methyl-4-pyridyl)porphyrin is adsorbed onto its outer surface in monolayer quantities, current rectification and charge trapping reactions are observed. The charge untrapping reactions are similar to those previously observed at redox polymer bilayer electrodes and are attributed to a kinetically fast cross reaction between double reduced viologens inside the zeolite and cobalt(II)porphyrin on the outer surface. Rotating disk experiments show that the porphyrin monolayer effectively seals up the zeolite against exchange of encapsulated viologens with solution-phase cations.

Research Organization:
Univ. of Texas, Austin (USA)
OSTI ID:
6926025
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:9; ISSN JPCHA
Country of Publication:
United States
Language:
English