Bulletin of the Korean Chemical Society

  • 제21권6호
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  • Pages.588-594
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  • 2000
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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In situ Structural Investigation of Iron Phthalocyanine Monolayer Adsorbed on Electrode Surface by X-ray Absorption Fine Structure

  • 발행 : 20000600
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초록

Structural changes of an iron phthalocyanine (FePC) monolayer induced by adsorption and externally applied potential on high area carbon surface have been investigated in situ by iron K-edge X-ray absorption fine structure (XAFS) in 0.5 M $H_2S0_4.$ Fine structures shown in the X-ray absorption near edge structure (XANES) for microcrystalline FePC decreased upon adsorption and further diminished under electrochemical conditions. Fe(II)PC(-2) showed a 1s ${\rightarrow}$ 4p transition as poorly resolved shoulder to the main absorption edge rather than a distinct peak and a weak 1s ${\rightarrow}$ 3d transition. The absorption edge position measured at half maximum was shifted from 7121.8 eV for Fe(lI)PC(-2) to 7124.8 eV for $[Fe(III)PC(-2)]^+$ as well as the 1s ${\rightarrow}$ 3d pre-edge peak being slightly enhanced. However, essentially no absorption edge shift was observed by the 1-electron reduction of Fe(Il)PC(-2), indicating that the species formed is $[Fe(II)PC(-3)]^-$. Structural parameters were obtained by analyzing extended X-ray absorption fine structure (EXAFS) oscillations with theoretical phases and amplitudes calculated from FEFF 6.01 using multiple-scattering theory. When applied to the powder FePC, the average iron-to-phthalocyanine nitrogen distance, d(Fe-$N_p$) and the coordination number were found to be 1.933 $\AA$ and 3.2, respectively, and these values are the same, within experimental error, as those reported ( $1.927\AA$ and 4). Virtually no structural changes were found upon adsorption except for the increased Debye-Wailer factor of $0.005\AA^2$ from $0.003\AA^2.$ Oxidation of Fe(II)PC(-2) to $[Fe(III)PC(-2)]^+$ yielded an increased d(Fe-Np) (1 $.98\AA)$ and Debye-Wailer factor $(0.005\AA^2).$ The formation of $[Fe(II)PC(-3)]^-$, however, produced a shorter d(Fe-$N_p$) of $1.91\AA$ the same as that of crystalline FePC within experimental error, and about the same DebyeWaller $factor(0.006\AA^2)$.

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