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Ionic Liquid Ordering at an Oxide Surface.

Michael Wagstaffe1, Mark J Jackman1, Karen L Syres2

  • 1School of Physics and Astronomy, The University of Manchester, Oxford Road, Manchester, M139PL, UK.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|July 27, 2016
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Summary

Ionic liquid [C4 C1 Im][BF4] interacts with titanium dioxide (TiO2) photoanodes, causing surface changes and ordered molecular arrangements at low concentrations. This research aids understanding of electrolyte-electrode interfaces in solar cells.

Keywords:
X-ray spectroscopyadsorptionionic liquidsphotoelectron spectroscopytitanium dioxide

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Area of Science:

  • Surface Science
  • Materials Chemistry
  • Electrochemistry

Background:

  • Ionic liquids are crucial in advanced energy systems like dye-sensitized solar cells.
  • Understanding electrolyte-electrode interactions is key to improving solar cell efficiency.
  • Anatase titanium dioxide (TiO2) is a widely used photoanode material.

Purpose of the Study:

  • To investigate the interaction between the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([C4 C1 Im][BF4]) and anatase TiO2.
  • To elucidate the initial chemical and structural changes at the interface.
  • To understand the ordering behavior of the ionic liquid on the TiO2 surface.

Main Methods:

  • Synchrotron radiation photoelectron spectroscopy (SRPES) was employed.
  • Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was utilized.
  • Combined spectroscopic techniques provided detailed surface analysis.

Main Results:

  • The tetrafluoroborate ([BF4]-) anion degrades upon interaction, leading to fluorine incorporation into oxygen vacancies on the TiO2 surface.
  • At low ionic liquid coverages, [C4 C1 Im][BF4] exhibits ordered adsorption on the anatase (101) surface.
  • The imidazolium ring orients at approximately 32±4° relative to the TiO2 surface due to electrostatic attraction.
  • At higher coverages, surface influence diminishes, and molecular ordering is lost.

Conclusions:

  • The initial interaction is characterized by anion degradation and surface functionalization.
  • Ordered adsorption of the ionic liquid occurs at low coverages, influenced by surface electrostatics.
  • Surface-ordering effects are coverage-dependent, diminishing as more ionic liquid is added.