• Title/Summary/Keyword: XANES

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In situ Structural Investigation of Iron Phthalocyanine Monolayer Adsorbed on Electrode Surface by X-ray Absorption Fine Structure

  • Kim, Seong Hyeon;Toshiaki Ohta;Gang, Gwang Hun
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.588-594
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    • 2000
  • 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 $factor(0.006\AA^2)$.

Mechanistic investigations on emission characteristics from g-C3N4, gC3N4@Pt and g-C3N4@Ag nanostructures using X-ray absorption spectroscopy

  • Sharma, Aditya;Varshney, Mayora;Chae, Keun Hwa;Won, Sung Ok
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1458-1464
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    • 2018
  • An improved method for the preparation of g-$C_3N_4$ is described. Currently, heating (> $400^{\circ}C$) of urea is the common method used for preparing the g-$C_3N_4$. We have found that sonication of melamine in $HNO_3$ solution, followed by washing with anhydrous ethanol, not only reduce the crystallite size of g-$C_3N_4$ but also facilitate intriguing electronic structure and photoluminescence (PL) properties. Moreover, loading of metal (Pt and Ag) nanoparticles, by applying the borohydride reduction method, has resulted in multicolor-emission from g-$C_3N_4$. With the help of PL spectra and local electronic structure study, at C K-edge, N K-edge, Pt L-edge and Ag K-edge by X-ray absorption spectroscopy (XAS), a precise mechanism of tunable luminescence is established. The PL mechanism ascribes the amendments in the transitions, via defect and/or metal states assimilation, between the ${\pi}^*$ states of tris-triazine ring of g-$C_3N_4$ and lone pair states of nitride. It is evidenced that interaction between the C/N 2p and metal 4d/5d orbitals of Ag/Pt has manifested a net detraction in the ${\delta}^*{\rightarrow}LP$ transitions and enhancement in the ${\pi}^*{\rightarrow}LP$ and ${\pi}^*{\rightarrow}{\pi}$ transitions, leading to broad PL spectra from g-$C_3N_4$ organic semiconductor compound.

Preparation of Wall Paper Coated with Modified TiO2 and Their Photocatalytic Effects for Removal of NO in Air (변조된 TiO2 광촉매를 이용한 벽지제조와 대기 중의 NO 제거 효과)

  • Kwon, Tae-Ri;Roo, Wan-Ho;Lee, Chul-Woo;Lee, Won-Mook
    • Korean Chemical Engineering Research
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    • v.43 no.1
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    • pp.1-8
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    • 2005
  • In this study, $TiO_2$ powders were prepared by hydro-thermal synthesis with titanium tetra isopropoxide. The prepared $TiO_2$ and the commercial $TiO_2$(P-25, Degussa) were by impregnating $H_2PtCl_6$ solution or the leached solution from the waste catalytic converter of automobile. Modified photocatalysts were analyzed by ICP-AES, UV-DRS, XRD, SEM. And band-gap energy of modified photo-catalyst was found to decreased to 1.76eV and basic structure was changed upon modification by leached solution. Modified photocatalysts were coated on the wallpaper after using mixed solution with adhesive materials(PVC). And then to know the modified photo catalysts tested the reactivity and quantum efficiency in the mixed gas with NO as reactants in the photo catalytic reactor. In the gas phase, photo-catalytic activity of NO was the highest for modified P-25 catalysts(P-25(w)) that P-25(w) was impregnated by leached solution of wasted catalytic converter.

Study of Iodide Adsorption on Organobentonite using X-ray Absorption Spectroscopy (X-선 흡수분광기를 이용한 유기벤토나이트의 요오드 흡착연구)

  • Yoon, Ji-Hae;Ha, Ju-Young;Hwang, Jin-Yeon;Hwang, Byoung-Hoon;Gordon E. Brown, Jr.
    • Journal of the Mineralogical Society of Korea
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    • v.22 no.1
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    • pp.23-34
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    • 2009
  • The adsorption of iodide on untreated bentonite and bentonites modified with organic cation (i.e., hexadecylpyridinium chloride monohydrate ($HDP^+$)) was investigated, and the organobentonites were characterized using uptake measurements, ${\mu}$-XRD, and electrophoretic mobilities measurement. Uptake measurements indicate that bentonite has a high affinity for $HDP^+$. Our ${\mu}$-XRD study indicates that organobentonites significantly expanded in basal spacing and organic cations were substantially intercalated into the interlayer spaces of bentonite. The electrophoretic mobility indicates that organobentonite tht is modified with organic cations in excess of the CEC of bentonite is completely different from untreated bentonite in the surface charge distribution. We found significant differences in adsorption capacities of iodide depending on the bentonite properties as follows: iodide adsorption capacities were 439 mmol/kg for the bentonite modified with $HDP^+$ at an equivalent amount corresponding to 200% of the CEC of bentonite whereas no adsorption of iodide was observed for the untreated bentonite. The molecular environments of iodine adsorbed on organobentonites were further studied using I K-edge and $L_{III}$-edge x-ray absorption spectroscopy (XAS). The X-ray absorption near-edge structure (XANES) of iodine spectra from organobentonites was similar to that of KI reference solution. Linear combination fitting of EXAFS data suggests the fraction of iodine reacted with the organic compound increased with increasing loading of the organic compound on organobentonites. In this study, we observed significant differences in the adsorption environments of iodide depending on the modified property of bentonite and suggest that an organobentonite has potential as reactive barrier material around a nuclear waste repository containing anionic radioactive iodide.