Surface-Induced Changes in the Thermochromic Transformation of an Ionic Liquid Cobalt Thiocyanate Complex
We demonstrate that a thermodynamic complex equilibrium within an ionic liquid film can be significantly influenced by the presence of the liquid-vacuum interface. Using surface-sensitive X-ray photoelectron spectroscopy, we find that the temperature-driven transition from the blue-colored tetrahedral [Co(II) (NCS)4]2- to the red-colored octahedral [Co(II) (NCS)6]4- complex already occurs within the outermost nanometers at around +4 °C as compared with -25 °C in the bulk. This thermochromic transformation in the near-surface region goes along with a loss in preferential surface orientation of free [SCN]- anions and with a pronounced decrease in the complex density; both effects are attributed to the formation of a weakly bound solvation shell around the [Co(II) (NCS)6]4- anion, leading to an effective complex dilution. Our results are not only relevant for high-surface area thin film systems, such as in sensor and catalysis applications, but also shed light on the role of ionic liquid surfaces in particular and liquid surfaces in general.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2017 |
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| Erschienen: |
2017 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:8 |
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| Enthalten in: |
The journal of physical chemistry letters - 8(2017), 6 vom: 16. März, Seite 1137-1141 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
May, Benjamin [VerfasserIn] |
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| Anmerkungen: |
Date Completed 05.02.2018 Date Revised 13.11.2018 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.jpclett.7b00142 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM269065911 |
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| 245 | 1 | 0 | |a Surface-Induced Changes in the Thermochromic Transformation of an Ionic Liquid Cobalt Thiocyanate Complex |
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| 500 | |a Date Revised 13.11.2018 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a We demonstrate that a thermodynamic complex equilibrium within an ionic liquid film can be significantly influenced by the presence of the liquid-vacuum interface. Using surface-sensitive X-ray photoelectron spectroscopy, we find that the temperature-driven transition from the blue-colored tetrahedral [Co(II) (NCS)4]2- to the red-colored octahedral [Co(II) (NCS)6]4- complex already occurs within the outermost nanometers at around +4 °C as compared with -25 °C in the bulk. This thermochromic transformation in the near-surface region goes along with a loss in preferential surface orientation of free [SCN]- anions and with a pronounced decrease in the complex density; both effects are attributed to the formation of a weakly bound solvation shell around the [Co(II) (NCS)6]4- anion, leading to an effective complex dilution. Our results are not only relevant for high-surface area thin film systems, such as in sensor and catalysis applications, but also shed light on the role of ionic liquid surfaces in particular and liquid surfaces in general | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Hönle, Michael |e verfasserin |4 aut | |
| 700 | 1 | |a Heller, Bettina |e verfasserin |4 aut | |
| 700 | 1 | |a Greco, Francesco |e verfasserin |4 aut | |
| 700 | 1 | |a Bhuin, Radha |e verfasserin |4 aut | |
| 700 | 1 | |a Steinrück, Hans-Peter |e verfasserin |4 aut | |
| 700 | 1 | |a Maier, Florian |e verfasserin |4 aut | |
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