Temperature-Dependent Surface Enrichment Effects in Binary Mixtures of Fluorinated and Non-Fluorinated Ionic Liquids.

Using angle-resolved X-ray photoelectron spectroscopy (ARXPS), we investigate the topmost nanometers of various binary ionic liquid (IL) mixtures at different temperatures in the liquid state. The mixtures consist of ILs with the same [PF6 ]- anion but two different cations, namely 3-methyl-1-(3,3,4,4,4-pentafluorobutyl)imidazolium hexafluorophosphate, [PFBMIm][PF6 ], and 1-butyl-3-methylimidazolium hexafluorophosphate, [C4 C1 Im][PF6 ], with 10, 25, 50 and 75 mol % content of [PFBMIm][PF6 ]. We observe a preferential enrichment of the fluorinated chain in the topmost layer, relative to the bulk composition, which is most pronounced for the lowest content of [PFBMIm][PF6 ]. Upon cooling the mixtures stepwise from 95 °C until surface charging effects in XPS indicate solidification, we observe a pronounced increase in surface enrichment of the fluorinated chain with decreasing temperature in the liquid state. In contrast to the mixtures with lower [PFBMIm][PF6 ] contents, cooling the 75 mol % mixture additionally shows an abrupt decrease of the fluorinated chain signal before complete solidification occurs, which is assigned to partial precipitation effects.

Potential Screening at Electrode/Ionic Liquid Interfaces from In Situ X-ray Photoelectron Spectroscopy.

A new approach to investigate potential screening at the interface of ionic liquids (ILs) and charged electrodes in a two-electrode electrochemical cell by in situ X-ray photoelectron spectroscopy has been introduced. Using identical electrodes, we deduce the potential screening at the working and the counter electrodes as a function of applied voltage from the potential change of the bulk IL, as derived from corresponding core level binding energy shifts for different IL/electrode combinations. For imidazolium-based ILs and Pt electrodes, we find a significantly larger potential screening at the anode than at the cathode, which we attribute to strong attractive interactions between the imidazolium cation and Pt. In the absence of specific ion/electrode interactions, asymmetric potential screening only occurs for ILs with different cation and anion sizes as demonstrated for an imidazolium chloride IL and Au electrodes, which we assign to the different thicknesses of the electrical double layers. Our results imply that potential screening in ILs is mainly established by a single layer of counterions at the electrode.

Few layer 2D pnictogens catalyze the alkylation of soft nucleophiles with esters.

Group 15 elements in zero oxidation state (P, As, Sb and Bi), also called pnictogens, are rarely used in catalysis due to the difficulties associated in preparing well-structured and stable materials. Here, we report on the synthesis of highly exfoliated, few layer 2D phosphorene and antimonene in zero oxidation state, suspended in an ionic liquid, with the native atoms ready to interact with external reagents while avoiding aerobic or aqueous decomposition pathways, and on their use as efficient catalysts for the alkylation of nucleophiles with esters. The few layer pnictogen material circumvents the extremely harsh reaction conditions associated to previous superacid-catalyzed alkylations, by enabling an alternative mechanism on surface, protected from the water and air by the ionic liquid. These 2D catalysts allow the alkylation of a variety of acid-sensitive organic molecules and giving synthetic relevancy to the use of simple esters as alkylating agents.

Cation Exchange at the Interfaces of Ultrathin Films of Fluorous Ionic Liquids on Ag(111).

In the context of applications with thin ionic liquid (IL) films on solid supports, we studied the ion distribution within mixed thin IL films by angle-resolved X-ray photoelectron spectroscopy. After the deposition of 1-methyl-3-octylimidazolium hexafluorophosphate, [C8C1Im][PF6], on top of a wetting layer (WL) of 3-methyl-1-(3,3,4,4,4-pentafluorobutyl)imidazolium hexafluorophosphate, [PFBMIm][PF6], on Ag(111) at room temperature (RT), we find a preferential enrichment of the [PFBMIm]+ cation at the IL/vacuum interface. In a similar deposition experiment at 82 K, this cation exchange at the IL/solid interface does not occur. Upon heating the film from 82 K to RT, we observe the replacement of [C8C1Im]+ by [PFBMIm]+ at the IL/vacuum interface between ∼160 and ∼220 K. No further changes in the surface composition were observed between 220 K and RT. Upon further heating the mixed IL film, we find the complete desorption of [PFBMIm][PF6] from the mixed film below 410 K, leaving a WL of pure [C8C1Im][PF6] on Ag(111), which desorbs until 455 K.

Anion Exchange at the Liquid/Solid Interface of Ultrathin Ionic Liquid Films on Ag(111).

Thin ionic liquid (IL) films play an important role in many applications. To obtain a better understanding of the ion distribution within IL mixture films, we sequentially deposited ultrathin layers of two ILs with the same cation but different anions onto Ag(111), and monitored their dynamic behaviour by angle-resolved X-ray photoelectron spectroscopy. Upon depositing [C8 C1 Im][PF6 ] on top of a wetting layer of [C8 C1 Im][Tf2 N] at room temperature (RT), we found a pronounced enrichment of the [Tf2 N]- anions at the IL/vacuum interface, due to a rapid anion exchange at the IL/solid interface. In contrast, at 90 K, the [Tf2 N]- anions remain at the IL/solid interface. Upon heating, we observe a rearrangement of the cations between 140 and 160 K, such that the octyl chains preferentially point towards the vacuum. Above 170 K, the ions start to become mobile, and at 220 K, the anion exchange is completed, with the [Tf2 N]- anions enriched at the IL/vacuum interface in the same way as found for deposition at RT. The temperature range for the anion exchange corresponds well to glass transition temperatures reported in literature. We propose two driving forces to be cooperatively responsible for the replacement/exchange of [Tf2 N]- at the IL/solid interface and its enrichment at the IL/vacuum interface. First, the adsorption energy of [C8 C1 Im][PF6 ] is significantly larger than that of [C8 C1 Im][Tf2 N], and second, the surface tension of [C8 C1 Im][Tf2 N] is lower than that of [C8 C1 Im][PF6 ].

Time-dependent changes in the growth of ultrathin ionic liquid films on Ag(111).

Various amounts of the ionic liquids (ILs) [C1C1Im][Tf2N] and [C8C1Im][Tf2N] were deposited in vacuo by physical vapour deposition (PVD) on single crystalline Ag(111) at room temperature and subsequently monitored by angle-resolved X-ray photoelectron spectroscopy (ARXPS) as a function of time. For very low coverages of up to one closed molecular layer, an initial wetting layer was rapidly formed for both ILs. Deposition of higher amounts of [C1C1Im][Tf2N] revealed an initial three-dimensional film morphology. On the time scale of hours, characteristic changes of the XPS signals were observed. These are interpreted as island spreading and a transformation towards a nearly two dimensional [C1C1Im][Tf2N] film as the final state. In contrast, a film morphology close to 2D was found from the very beginning for [C8C1Im][Tf2N] deposited on Ag(111) demonstrating the influence of the alkyl chain length on the growth kinetics. These studies also highlight the suitability of time-resolved ARXPS for the investigation of IL/solid interfaces, which play a crucial role in IL thin film applications such as in catalysis, sensor, lubrication, and coating technologies.

Surface Enrichment in Equimolar Mixtures of Non-Functionalized and Functionalized Imidazolium-Based Ionic Liquids.

For equimolar mixtures of ionic liquids with imidazolium-based cations of very different electronic structure, we observe very pronounced surface enrichment effects by angle-resolved X-ray photoelectron spectroscopy (XPS). For a mixture with the same anion, that is, 1-methyl-3-octylimidazolium hexafluorophosphate+1,3-di(methoxy)imidazolium hexafluorophosphate ([C8 C1 Im][PF6 ]+[(MeO)2 Im][PF6 ]), we find a strong enrichment of the octyl chain-containing [C8 C1 Im]+ cation and a corresponding depletion of the [(MeO)2 Im]+ cation in the topmost layer. For a mixture with different cations and anions, that is, [C8 C1 Im][Tf2 N]+[(MeO)2 Im][PF6 ], we find both surface enrichment of the [C8 C1 Im]+ cation and the [Tf2 N]- (bis[(trifluoromethyl)sulfonyl]imide) anion, while [(MeO)2 Im]+ and [PF6 ]- are depleted from the surface. We propose that the observed behavior in these mixtures is due to a lowering of the surface tension by the enriched components. Interestingly, we observe pronounced differences in the chemical shifts of the imidazolium ring signals of the [(MeO)2 Im]+ cations as compared to the non-functionalized cations. Calculations of the electronic structure and the intramolecular partial charge distribution of the cations contribute to interpreting these shifts for the two different cations.

Probing the Surface Tension of Ionic Liquids Using the Langmuir Principle.

At 298 K, the surface tension of ionic liquids (ILs) of the 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide series, [C nC1Im][NTf2], ranges from around 35 mN·m-1 for [C2C1Im][NTf2] to just below 30 mN·m-1 for [C12C1Im][NTf2]. However, the decrease rate along the series is not constant: a large decrease from [C2C1Im][NTf2] to [C8C1Im][NTf2] is followed by almost constant values from [C8C1Im][NTf2] to [C12C1Im][NTf2]. Such behavior is hard to interpret from a molecular point of view without suitable information about the free-surface structure of the different ILs. In this work, we have successfully used the Langmuir principle in combination with structural data obtained from angle-resolved X-ray photoelectron spectroscopy experiments and molecular dynamics simulations, to predict the correct surface tension trend along the IL series. The concepts unveiled for this particular homologous IL family can be easily extended to other systems.