Charge transfer and molecular distribution of Ru(bpy)2+3 complex dispersed in a Nafion® membrane as studied by in-situ spectrocyclic voltammetry

Yagi, Masayuki; Nagai, Keiji; Onikubo, Toshikazu; Kaneko, Masao

doi:10.1016/0022-0728(94)03681-r

Cited by 53 publications

(44 citation statements)

References 31 publications

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“…In our previous reports the electron transfer in the ) and reduction of methylviologen (MV 2 /MV Á ) in Nafion was studied [27,28,41,42]. The electron transfer in the reduction of MV 2 to MV Á occurred by a physical diffusion mechanism, although the redox species are incorporated into the Nafion by a rather strong electrostatic interaction.…”

Section: Discussionmentioning

confidence: 97%

“…When the MV 2 was anchored onto the polymer framework by a chemical bond, the electron transfer in the reduction of MV 2 to MV Á occurred through a hopping mechanism [42]. In the oxidation of Ru(bpy) 3 2 to Ru(bpy) 3 3 the charge transfer took place by a hopping mechanism [27,28,43], but in the reduction of Ru(bpy) 3 3 to Ru(bpy) 3 2 it took place by a diffusion mechanism [59]. The results indicated that the interaction of the product with the matrix is the deciding factor for the mechanism.…”

Section: Discussionmentioning

confidence: 99%

“…In this case the electron transfer occurs through an electron-hopping mechanism. Otherwise, physical diffusion takes place [24][25][26][27][28]. In the present work, tetraphenylporphyrin cobalt was employed as a redox species because of its potential application as a catalyst of proton reduction as well as its clear spectral change following multi-step redox reactions [29][30][31].…”

Section: Introductionmentioning

confidence: 99%

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Electron Transfer in the Reduction of Cobalt Porphyrin Incorporated into Nafion and Poly(4-vinylpyridine-co-styrene) Films

Zhao

Zhang

Abe

et al. 1999

J. Porphyrins Phthalocyanines

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Potential step chronoamperospectrometry (PSCAS) measurement was carried out to investigate the one-electron transfer in the reduction of tetraphenylporphyrin cobalt(III) ([ Co III TPP (−2)]+) incorporated into a Nafion or poly(4-vinylpyridine-co-styrene) (P(VP-St)) film coated on an ITO electrode. The electron transfer of the redox centers in the two systems occurred by a physical diffusion mechanism. The fraction of the electroactive complex (R ct ) was independent of the CoTPP concentration in P(VP-St) but decreased with increasing CoTPP concentration in Nafion, especially at high concentrations. In both systems the apparent diffusion coefficient Dapp decreased with increasing CoTPP concentration. The Dapp value in Nafion (1.6 × 10−8 cm 2 s −1 at 0.02 M) was much higher than that in P(VP-St) (1.1 × 10−10 cm 2 s −1 at 0.02 M). The difference in the electron transfer process in the two systems was ascribed to the interaction of the redox center with the polymer framework, the morphology of the polymer matrix, the localization of the redox species in the hydrophilic/hydrophobic region, and the counterion migration under the potential step.

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Section: Discussionmentioning

confidence: 97%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electron Transfer in the Reduction of Cobalt Porphyrin Incorporated into Nafion and Poly(4-vinylpyridine-co-styrene) Films

Zhao

Zhang

Abe

et al. 1999

J. Porphyrins Phthalocyanines

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“…This film was then placed in an aqueous solution of 4 mM [Os(bpy) 2 Pic] þ for a given length of time. Breaking in of the films, which involves firsttime exposure of the film to the electrolyte was carried out with redox cycling in any given electrolyte at 0.1 V s À1 for 30 cycles, until stable currents were achieved (with 7% increase in electroactivity).…”

Section: Electrode Preparation 1 (A)mentioning

confidence: 99%

“…Firstly the properties of the mediator, [Os(bpy) 2 Pic] þ within the film are investigated before inclusion of carbon nanotubes and an examination of film properties at SWCNT modified electrodes.…”

mentioning

confidence: 99%

Investigation into Charge Transport Dynamics of [Os(bpy)₂(picolinate)]Cl Nafion Films

Warren¹,

McCormac²,

Mihaylova

et al. 2006

Electroanalysis

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) and the effect of %loading of redox material was determined for three electrolytes over a range of concentrations. The data obtained implies that charge transfer within the film occurs via a redox site diffusion mechanism. The concentration of redox sites was determined using an approximate film thickness of 7 mm, as determined from profilometry studies. Experiments were also performed using immobilized carbon nanotubes within the redox film in order to examine the impact of the increased surface area and conductivity. The presence of the carbon nanotubes had the effect of doubling the surface coverage values and enhancing D CT 1/2 C M values from 1.9 Â 10 À9 to 16.1 Â 10 À9 mol cm À1 s À1.

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Charge Transfer of Tetraphenylporphyrin Zinc Complexes Incorporated in a Poly(2-vinylpyridine) Matrix

Zhang

Abe

Kaneko

1998

J. Porphyrins Phthalocyanines

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An indium tin oxide (ITO) electrode was coated by a poly(2-vinylpyridine) (P-2VP) film incorporating tetraphenylporphyrin zinc ( ZnTPP ) as a redox center. A cyclic voltammogram (CV) exhibited a couple of redox waves at 0.7 V (vs Ag / AgCl ). The potential-step chronoamperospectrometry (PSCAS) measurement was carried out on the modified electrode immersed in a 0.1 M LiClO 4 aqueous solution at pH 3.5 under argon atmosphere. Assuming a random distribution of the redox species in the macromolecular structure, the charge transfer distance between the adjacent ZnTPP complexes was obtained as 1.08 nm. The charge hopping distance between the redox centers (1.01 nm) and the bounded motion distance (0.07 nm after 2h) were obtained according to their different response time in the electrochemical measurement. Considering the contributions from both the charge hopping and bounded motion, the second order rate constant of electron hopping was 4.1 × 104 M−1s−1.

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Charge transfer and molecular distribution of Ru(bpy)2+3 complex dispersed in a Nafion® membrane as studied by in-situ spectrocyclic voltammetry

Cited by 53 publications

References 31 publications

Electron Transfer in the Reduction of Cobalt Porphyrin Incorporated into Nafion and Poly(4-vinylpyridine-co-styrene) Films

Electron Transfer in the Reduction of Cobalt Porphyrin Incorporated into Nafion and Poly(4-vinylpyridine-co-styrene) Films

Investigation into Charge Transport Dynamics of [Os(bpy)₂(picolinate)]Cl Nafion Films

Charge Transfer of Tetraphenylporphyrin Zinc Complexes Incorporated in a Poly(2-vinylpyridine) Matrix

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Charge transfer and molecular distribution of Ru(bpy)2+3 complex dispersed in a Nafion® membrane as studied by in-situ spectrocyclic voltammetry

Cited by 53 publications

References 31 publications

Electron Transfer in the Reduction of Cobalt Porphyrin Incorporated into Nafion and Poly(4-vinylpyridine-co-styrene) Films

Electron Transfer in the Reduction of Cobalt Porphyrin Incorporated into Nafion and Poly(4-vinylpyridine-co-styrene) Films

Investigation into Charge Transport Dynamics of [Os(bpy)2(picolinate)]Cl Nafion Films

Charge Transfer of Tetraphenylporphyrin Zinc Complexes Incorporated in a Poly(2-vinylpyridine) Matrix

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Investigation into Charge Transport Dynamics of [Os(bpy)₂(picolinate)]Cl Nafion Films