Understanding the Buoy Effect of Surface-Enriched Pt Complexes in Ionic Liquids: A Combined ARXPS and Pendant Drop Study.

Recently, we demonstrated that Pt catalyst complexes dissolved in the ionic liquid (IL) [C C Im][PF ] can be deliberately enriched at the IL surface by introducing perfluorinated substituents, which act like buoys dragging the metal complex towards the surface. Herein, we extend our previous angle-resolved X-ray photoelectron spectroscopy (ARXPS) studies at complex concentrations between 30 and 5 % down to 1 % and present complementary surface tension pendant drop (PD) measurements under ultraclean vacuum conditions. This combination allows for connecting the microscopic information on the IL/gas interface derived from ARXPS with the macroscopic property surface tension.

Adsorption and thermal evolution of [CCIm][TfN] on Pt(111).

In the context of ionic liquid (IL)-assisted catalysis, we have investigated the adsorption and thermal evolution of the IL 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([CCIm][TfN]) on Pt(111) between 100 and 800 K by angle-resolved X-ray photoelectron spectroscopy and scanning tunneling microscopy. Defined amounts of IL in the coverage range of a complete first wetting layer were deposited at low temperature (100-200 K), and subsequently heated to 300 K, or directly at 300 K. At 100 K, the IL adsorbs as an intact disordered layer.

Time- and Temperature-Dependent Growth Behavior of Ionic Liquids on Au(111) Studied by Atomic Force Microscopy in Ultrahigh Vacuum.

We deposited defined amounts of [CCIm][TfN] on Au(111) at different temperatures and investigated the morphology and wetting behavior of the deposited films by atomic force microscopy. For multilayer coverages, we observe a drastically different growth behavior when comparing deposition at room temperature (RT) and deposition below 170 K followed by slow annealing to RT. Upon deposition at RT, we find the formation of 2-30 nm high and 50-500 nm wide metastable 3D droplets on top of a checkerboard-type wetting layer.

Growth of Multilayers of Ionic Liquids on Au(111) Investigated by Atomic Force Microscopy in Ultrahigh Vacuum.

Understanding the growth of ultrathin films of ionic liquids (ILs) on metal surfaces is of highest relevance for a variety of applications. We present a detailed study of the growth of the wetting layer and successive multilayers of 1,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([CCIm][TfN]) on Au(111). By atomic force microscopy (AFM) in ultrahigh vacuum, we follow the temperature-dependent behavior between 110 and 300 K at defined coverages.

Atomic Force and Scanning Tunneling Microscopy of Ordered Ionic Liquid Wetting Layers from 110 K up to Room Temperature.

Ionic liquids (ILs) are used as ultrathin films in many applications. We studied the nanoscale arrangement within the first layer of 1,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([CCIm] [TfN]) on Au(111) between 400 and 110 K in ultrahigh vacuum by scanning tunneling and noncontact atomic force microscopy with molecular resolution. Compared to earlier studies on similar ILs, a different behavior is observed, which we attribute to the small size and symmetrical shape of the cation: (a) In both AFM and STM only the anions are imaged; (b) only long-range-ordered but no amorphous phases are observed; (c) the hexagonal room-temperature phase melts 30-50 K above the IL's bulk melting point; (d) at 110 K, striped and hexagonal superstructures with two and three ion pairs per unit cell, respectively, are found.