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It is a frequent observation that the diffusion coefficient measured by chronocoulometry is larger than that observed using cyclic voltammetry. This difference may reflect the variation in the density of redox centers through the film thickness causing an increased intersite separation and lower rates of charge transport. The redox composition of a significantly larger fraction of the layer is switched in the slower cyclic voltammetry experiments than in chronocoulometry. Intercalation of charge compensating counterions in the SAM may occur under these conditions impairing the charge transport. The diffusion coefficients derived from impedance measurements are assumed to be higher for a similar reason. See: Hogan, C. F.; Forster, R. J. Analytica Chimica Acta 1999, 396, 13-21.
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44
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33645466677
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note
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2+ increases the size of the ruthenium compound and decreases the accessibility of the surface bound complex to charge compensation ions, which could lower the rate of cross-surface charge percolation.
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45
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Wang, P.; Zakeeruddin, S. M.; Comte, P.; Charvet, R.; Humphry-Baker, R.; Grätzel, M. J. Phys. Chem. B 2003, 107, 14336-14341.
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46
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33645462008
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note
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2 film is comparable to complex 2. Whereas the uptake of complex 2 is 5.7% higher than that of 1.
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