Transition of Molecule Orientation during Adsorption of Terephthalic Acid on Rutile TiO2(110)
The coverage-dependent mode of adsorption of terephthalic acid [C6H4(COOH)2, TPA] on rutile TiO2(110) was investigated by means of noncontact atomic force microscopy (NC-AFM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy under ultrahigh vacuum conditions at room temperature. In...
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Published in | Journal of physical chemistry. C Vol. 113; no. 40; pp. 17471 - 17478 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
08.10.2009
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Abstract | The coverage-dependent mode of adsorption of terephthalic acid [C6H4(COOH)2, TPA] on rutile TiO2(110) was investigated by means of noncontact atomic force microscopy (NC-AFM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy under ultrahigh vacuum conditions at room temperature. Individual molecules are observed to adsorb in an disordered, flat-lying geometry at low coverages up to ∼0.3 monolayer (ML). The molecules are immobile at room temperature, implying a diffusion barrier larger than 0.8 eV. This rather high value might be explained by anchoring to surface defect sites. A transition from flat-lying to upright-oriented molecules is revealed by NEXAFS when saturation coverage is achieved. High-resolution NC-AFM images reveal two different structures at coverages between ∼0.8 and 1 ML: (i) a well-ordered (2 × 1) structure and (ii) a structure of single and paired rows oriented along the [001] crystallographic direction. The latter structure might originate from a pairwise interaction of two neighboring molecules through the top carboxyl groups. Further increase in the exposure results in a saturation of the corresponding signal in the NEXAFS spectra, revealing that the growth of TPA on TiO2(110) at room temperature is self-limiting. |
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AbstractList | The coverage-dependent mode of adsorption of terephthalic acid [C6H4(COOH)2, TPA] on rutile TiO2(110) was investigated by means of noncontact atomic force microscopy (NC-AFM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy under ultrahigh vacuum conditions at room temperature. Individual molecules are observed to adsorb in an disordered, flat-lying geometry at low coverages up to ∼0.3 monolayer (ML). The molecules are immobile at room temperature, implying a diffusion barrier larger than 0.8 eV. This rather high value might be explained by anchoring to surface defect sites. A transition from flat-lying to upright-oriented molecules is revealed by NEXAFS when saturation coverage is achieved. High-resolution NC-AFM images reveal two different structures at coverages between ∼0.8 and 1 ML: (i) a well-ordered (2 × 1) structure and (ii) a structure of single and paired rows oriented along the [001] crystallographic direction. The latter structure might originate from a pairwise interaction of two neighboring molecules through the top carboxyl groups. Further increase in the exposure results in a saturation of the corresponding signal in the NEXAFS spectra, revealing that the growth of TPA on TiO2(110) at room temperature is self-limiting. |
Author | Wöll, Ch Kühnle, A Naboka, M Nefedov, A Nimmrich, M Rahe, P |
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Title | Transition of Molecule Orientation during Adsorption of Terephthalic Acid on Rutile TiO2(110) |
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