Assessing Solid Catalysts with Ionic Liquid Layers (SCILL) from Molecular Dynamics Simulations: On the role of local charge polarization.

Recent developments in molecular mechanics modelling of metal catalyst surfaces with interfaces to complex ad-layers or bulk liquids enable the study of 10 nm scale systems by molecular dynamics simulations of up to microseconds. Therein, electronic polarization as otherwise benchmarked by quantum calculations is mimicked via atom-centered partial charges that are adjusted dynamically to account for changes in local environment. Apart from thermal fluctuations, this encompasses molecule association and dissociation processes as well as externally applied voltage. Here, we elaborate the concept of employing the charge equilibration method to the molecular dynamics simulation of solid catalysts, namely metal surfaces and substrate-supported metal nanoparticles. This showcases the association of reactants and their interplay with local charge polarization upon co-adsorption of ionic liquids or application of external voltage - thus paving the way to understanding complex interfaces in (electro-)catalysis from molecular dynamics simulation.

Self-Assembled Supported Ionic Liquids.

Separation and reuse of the catalytically active metal complexes are persistent issues in homogeneous catalysis. Supported Ionic Liquid Phase (SILP) catalysts, where the catalytic center is dissolved in a thin film of a stable ionic liquid, deposited on a solid support, present a promising alternative. However, the dissolution of the metal center in the film leaves little control over its position and its activity. We present here four novel, task-specific ionic liquids [FPhn ImH R]I (n=1, 2; R=PEG2 , C12 H25 ), designed to self-assemble on a silica surface without any covalent bonding and offering a metal binding site in a controlled distance to the support. Advanced multinuclear solid-state NMR spectroscopic techniques under Magic Angle Spinning, complemented by molecular dynamics (MD) simulations, allow us to determine their molecular conformation when deposited inside SBA-15 as a model silica support. We provide here conceptual proof for a rational design of ionic liquids self-assembling into thin films, opening an avenue for a second, improved generation of SILP catalysts.

Evolution of Surface Tension and Hansen Parameters of a Homologous Series of Imidazolium-Based Ionic Liquids.

In this study, we systematically analyze the surface tension and Hansen solubility parameters (HSPs) of imidazolium-based ionic liquids (ILs) with different anions ([NTf2]-, [PF6]-, [I]-, and [Br]-). These anions are combined with the classical 1-alkyl-3-methyl-substituted imidazolium cations ([CnC1Im]+) and a group of oligoether-functionalized imidazolium cations ([(mPEGn)2Im]+) based on methylated polyethylene glycol (mPEGn). In detail, the influences of the length of the alkyl- and the mPEGn-chain, the anion size, and the water content are investigated experimentally. For [CnC1Im]+-based ILs, the surface tension decreases with increasing alkyl chain length in all cases, but the magnitude of this decrease depends on the size of the anion ([NTf2]- < [PF6]- < [Br]- ≤ [I]-). Molecular dynamics (MD) simulations on [CnC1Im]+-based ILs indicate that these differences are caused by the interplay of charged and uncharged domains, in particular in the different anions, which affects the ability of the alkyl chains of the cation to orient toward the liquid-gas interface. An increase in the mPEGn-chain length of the [(mPEGn)2Im][A] ILs does not significantly influence the surface tension. These changes upon variation of the cation/anion combination do not correlate with the evolution of the HSPs for the two sets of ILs. Finally, our data suggest that significant water contents up to water mole fractions of x(H2O) = 0.25 do not significantly affect the surface tension of the studied binary IL-water mixtures.

Structure Formation in an Ionic Liquid Wetting Layer: A Combined STM, IRAS, DFT and MD Study of [C2 C1 Im][OTf] on Au(111).

In a solid catalyst with ionic liquid layer (SCILL), ionic liquid (IL) coatings are used to improve the selectivity of noble metal catalysts. To understand the origins of this selectivity control, we performed model studies by surface science methods in ultrahigh vacuum (UHV). We investigated the growth and thermal stability of ultrathin IL films by infrared reflection absorption spectroscopy (IRAS). We combined these experiments with scanning tunneling microscopy (STM) to obtain information on the orientation of the ions, the interactions with the surface, the intermolecular interactions, and the structure formation. Additionally, we performed DFT calculations and molecular dynamics (MD) simulations to interpret the experimental data. We studied the IL 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [C2 C1 Im][OTf] on Au(111) surfaces. We observe a weakly bound multilayer of [C2 C1 Im][OTf], which is stable up to 390 K, while the monolayer desorbs at ∼450 K. [C2 C1 Im][OTf] preferentially adsorbs at the step edges and elbows of the herringbone reconstruction of Au(111). The anion adsorbs via the SO3 group with the molecular axis perpendicular to the surface. At low coverage, the [C2 C1 Im][OTf] crystallizes in a glass-like 2D phase with short-range order. At higher coverage, we observe a phase transition to a 6-membered ring structure with long-range order.