Vectorial electron transport at ion-exchanged zeolite-Y-modified electrodes

Zhuyin Li; Thomas E. Mallouk

doi:10.1021/j100287a029

Vectorial electron transport at ion-exchanged zeolite-Y-modified electrodes

Zhuyin Li
, Thomas E. Mallouk

Chemistry

Research output: Contribution to journal › Article › peer-review

99 Scopus citations

Abstract

Chemically modified SnO₂ electrodes were prepared, using zeolite Y which had been ion-exchanged with a metal tris(bipyridyl) complex, M(bpy)₃²⁺ (M = Ru, Os), and a metallocene cation, M(CpR)₂⁺ or M(Cp)(CpR)⁺ (M = Co, Fe; Cp = η₅-cyclopentadienyl; R = -H, -CH₃, -NH₂, -COOCH₃, -CH₂N(CH₃)₃). The rate of charge transfer between the electrode and the metallocene contained within the zeolite is enhanced at least tenfold by adsorbing M(bpy)₃²⁺ onto the zeolite surface. Both oxidation and reduction of the metallocene are facile if the potentials of the M(bpy)₃²⁺ and M(CpR)₂⁺ couples are matched, but only one of these processes occurs if the potentials are dissimilar. This behavior is attributed to a rapid electron-transfer cross reaction between the two complexes. The equilibrium potentials of the zeolite-bound M(CpR)₂^+/0 couples were found to be 300-600-mV positive of the corresponding potentials in polar organic solvents. The charge transport diffusion coefficient for Co(CpCH₃)₂^+/0 in zeolite Y, from linear sweep voltammetry, was found to be ca. 2 × 10^-10 cm²/s.

Original language	English (US)
Pages (from-to)	643-648
Number of pages	6
Journal	Journal of physical chemistry
Volume	91
Issue number	3
DOIs	https://doi.org/10.1021/j100287a029
State	Published - 1987

All Science Journal Classification (ASJC) codes

General Engineering
Physical and Theoretical Chemistry

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@article{6774e47881234ba498ced7a596abfb39,

title = "Vectorial electron transport at ion-exchanged zeolite-Y-modified electrodes",

abstract = "Chemically modified SnO2 electrodes were prepared, using zeolite Y which had been ion-exchanged with a metal tris(bipyridyl) complex, M(bpy)32+ (M = Ru, Os), and a metallocene cation, M(CpR)2+ or M(Cp)(CpR)+ (M = Co, Fe; Cp = η5-cyclopentadienyl; R = -H, -CH3, -NH2, -COOCH3, -CH2N(CH3)3). The rate of charge transfer between the electrode and the metallocene contained within the zeolite is enhanced at least tenfold by adsorbing M(bpy)32+ onto the zeolite surface. Both oxidation and reduction of the metallocene are facile if the potentials of the M(bpy)32+ and M(CpR)2+ couples are matched, but only one of these processes occurs if the potentials are dissimilar. This behavior is attributed to a rapid electron-transfer cross reaction between the two complexes. The equilibrium potentials of the zeolite-bound M(CpR)2+/0 couples were found to be 300-600-mV positive of the corresponding potentials in polar organic solvents. The charge transport diffusion coefficient for Co(CpCH3)2+/0 in zeolite Y, from linear sweep voltammetry, was found to be ca. 2 × 10-10 cm2/s.",

author = "Zhuyin Li and Mallouk, \{Thomas E.\}",

year = "1987",

doi = "10.1021/j100287a029",

language = "English (US)",

volume = "91",

pages = "643--648",

journal = "Journal of physical chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "3",

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TY - JOUR

T1 - Vectorial electron transport at ion-exchanged zeolite-Y-modified electrodes

AU - Li, Zhuyin

AU - Mallouk, Thomas E.

PY - 1987

Y1 - 1987

N2 - Chemically modified SnO2 electrodes were prepared, using zeolite Y which had been ion-exchanged with a metal tris(bipyridyl) complex, M(bpy)32+ (M = Ru, Os), and a metallocene cation, M(CpR)2+ or M(Cp)(CpR)+ (M = Co, Fe; Cp = η5-cyclopentadienyl; R = -H, -CH3, -NH2, -COOCH3, -CH2N(CH3)3). The rate of charge transfer between the electrode and the metallocene contained within the zeolite is enhanced at least tenfold by adsorbing M(bpy)32+ onto the zeolite surface. Both oxidation and reduction of the metallocene are facile if the potentials of the M(bpy)32+ and M(CpR)2+ couples are matched, but only one of these processes occurs if the potentials are dissimilar. This behavior is attributed to a rapid electron-transfer cross reaction between the two complexes. The equilibrium potentials of the zeolite-bound M(CpR)2+/0 couples were found to be 300-600-mV positive of the corresponding potentials in polar organic solvents. The charge transport diffusion coefficient for Co(CpCH3)2+/0 in zeolite Y, from linear sweep voltammetry, was found to be ca. 2 × 10-10 cm2/s.

AB - Chemically modified SnO2 electrodes were prepared, using zeolite Y which had been ion-exchanged with a metal tris(bipyridyl) complex, M(bpy)32+ (M = Ru, Os), and a metallocene cation, M(CpR)2+ or M(Cp)(CpR)+ (M = Co, Fe; Cp = η5-cyclopentadienyl; R = -H, -CH3, -NH2, -COOCH3, -CH2N(CH3)3). The rate of charge transfer between the electrode and the metallocene contained within the zeolite is enhanced at least tenfold by adsorbing M(bpy)32+ onto the zeolite surface. Both oxidation and reduction of the metallocene are facile if the potentials of the M(bpy)32+ and M(CpR)2+ couples are matched, but only one of these processes occurs if the potentials are dissimilar. This behavior is attributed to a rapid electron-transfer cross reaction between the two complexes. The equilibrium potentials of the zeolite-bound M(CpR)2+/0 couples were found to be 300-600-mV positive of the corresponding potentials in polar organic solvents. The charge transport diffusion coefficient for Co(CpCH3)2+/0 in zeolite Y, from linear sweep voltammetry, was found to be ca. 2 × 10-10 cm2/s.

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JO - Journal of physical chemistry

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Vectorial electron transport at ion-exchanged zeolite-Y-modified electrodes

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