In this work, we perform atomic force microscopy (AFM) experiments to evaluate in situ the dependence of the structural morphology of trihexyltetradecylphosphonium bis(2-ethylhexyl) phosphate ([P 6,6,6,14 ][DEHP]) ionic liquid (IL) on applied pressure. The experimental results obtained upon sliding a diamond-like-carbon-coated silicon AFM tip on mechanically polished steel at an applied pressure up to 5.5 ± 0.3 GPa indicate a structural transition of confined [P 6,6,6,14 ][DEHP] molecules. This pressure-induced morphological change of [P 6,6,6,14 ][DEHP] IL leads to the generation of a lubricious, solid-like interfacial layer, whose growth rate increases with applied pressure and temperature. The structural variation of [P 6,6,6,14 ][DEHP] IL is proposed to derive from the well-ordered layering of the polar groups of ions separated by the apolar tails. These results not only shed new light on the structural organization of phosphonium-based ILs under elevated pressure, but also provide novel insights into the normal pressure-dependent lubrication mechanisms of ILs in general.
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Direct observation of the double-layering quantized growth of mica-confined ionic liquids
Since the interface between ionic liquids (ILs) and solids always plays a critical role in important applications such as coating, lubrication, energy storage and catalysis, it is essential to unravel the molecular structure and dynamics of ILs confined to solid surfaces. Here we report direct observation of a unique double-layering quantized growth of three IL ( i.e. [Emim][FAP], [Bmim][FAP] and [Hmim][FAP]) nanofilms on mica. AFM results show that the IL nanofilms initially grow only by covering more surface areas at the constant film thickness of 2 monolayers (ML) until a quantized increase in the film thickness by another 2 ML occurs. Based on the AFM results, we propose a double-layering model describing the molecular structure of IL cations and anions on the mica surface. The interesting double-layering structure can be explained as the result of several competing interactions at the IL–mica interface. Meanwhile, the time-dependent AFM results indicate that the topography of IL nanofilms could change with time and mobility of the nanofilm is lower for ILs with longer alkyl chains, which can be attributed to the stronger solvophobic interaction. The findings here have important implications on the molecular structure and dynamics of ILs confined to solid surfaces.
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- Award ID(s):
- 1904486
- NSF-PAR ID:
- 10332718
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 13
- Issue:
- 42
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 17961 to 17971
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1nr05437f
