Integrative studies of ionic liquid interface layers: bridging experiments, theoretical models and simulations.

Ionic liquids (ILs) are a class of salts existing in the liquid state below 100 °C, possessing low volatility, high thermal stability as well as many highly attractive solvent and electrochemical capabilities, etc., making them highly tunable for a great variety of applications, such as lubricants, electrolytes, and soft functional materials. In many applications, ILs are first either physi- or chemisorbed on a solid surface to successively create more functional materials. The functions of ILs at solid surfaces can differ considerably from those of bulk ILs, mainly due to distinct interfacial layers with tunable structures resulting in new ionic liquid interface layer properties and enhanced performance. Due to an almost infinite number of possible combinations among the cations and anions to form ILs, the diversity of various solid surfaces, as well as different external conditions and stimuli, a detailed molecular-level understanding of their structure-property relationship is of utmost significance for a judicious design of IL-solid interfaces with appropriate properties for task-specific applications. Many experimental techniques, such as atomic force microscopy, surface force apparatus, and so on, have been used for studying the ion structuring of the IL interface layer. Molecular Dynamics simulations have been widely used to investigate the microscopic behavior of the IL interface layer. To interpret and clarify the IL structure and dynamics as well as to predict their properties, it is always beneficial to combine both experiments and simulations as close as possible. In another theoretical model development to bridge the structure and properties of the IL interface layer with performance, thermodynamic prediction & property modeling has been demonstrated as an effective tool to add the properties and function of the studied nanomaterials. Herein, we present recent findings from applying the multiscale triangle "experiment-simulation-thermodynamic modeling" in the studies of ion structuring of ILs in the vicinity of solid surfaces, as well as how it qualitatively and quantitatively correlates to the overall ILs properties, performance, and function. We introduce the most common techniques behind "experiment-simulation-thermodynamic modeling" and how they are applied for studying the IL interface layer structuring, and we highlight the possibilities of the IL interface layer structuring in applications such as lubrication and energy storage.

Lattice Compressive Strain of Co3O4 Induced by Synthetic Solvents Promotes Efficient Oxidation of Benzene at Low Temperature.

A series of Co3O4 with different surface defective structures were prepared by the solvothermal method and tested for the activity of benzene oxidation. The characterizations revealed that the synthetic solvent had a dramatic effect on the composition of Co3O4 precursors as well as the physicochemical properties of Co3O4. Although all Co3O4 exhibited a cubic spinel structure, Co3O4 prepared with triethylene glycol (Co-TEG) had the highest compressive strain due to the nature of high viscosity of triethylene glycol. These in turn affected the surface chemical structure and the low-temperature redox properties. Co-TEG exhibited the best benzene oxidation activity and showed excellent stability and good water resistance. In situ diffuse reflectance infrared Fourier transform spectroscopy was used to study the oxidation process of benzene. It was found that Co-TEG with more defective structures had abundant surface adsorbed oxygen and active lattice oxygen, which promoted the conversion of benzene and the corresponding intermediates at low temperature.

CO2/CH4 Separation via Carbon-Based Membrane: The Dynamic Role of Gas-Membrane Interface.

Membrane separation is considered one of the most promising CO2/CH4 separation technologies currently available because it is a safe, environment-friendly, and economical method. However, the inability of membrane materials to reconcile the trade-off between permeability and permeation selectivity limits their further applications; moreover, the mechanism underlying this process is unclear, which is mainly determined by the performance of gas adsorption and diffusion. Therefore, this paper describes the effect of gas adsorption and diffusion on membrane separation by assessing the fundamental gas-membrane and gas-gas interactions. Combining molecular simulation methods (Monte Carlo and molecular dynamics simulation) and a thermodynamic model called "linearized nonequilibrium thermodynamic transfer model", we investigate the permeability and permeation selectivity for CO2/CH4 in five carbon-based membranes and propose a general method for screening membrane materials. The interaction-dominated mechanism derived in this work provides new insights into membrane separation and facilitates the screening of high-performance membrane materials.

Effect analysis of pore wall thickness, pore size, and functional group of activated carbon on adsorption behavior based on molecular simulation.

To effectively investigate the influence of activated carbon on the adsorption of volatile organic compounds (VOCs), physical and chemical factors of activated carbon including pore wall thickness, pore size, and functional groups were studied using grand canonical Monte Carlo (GCMC) simulation. In addition, benzene and acetone were taken as two representative components of VOCs. Simulation results was presented by the changes in characteristics of benzene and acetone. The results show that at the saturated vapor pressure (P0), the adsorption density hardly varies with the mentioned factors of activated carbon. Differently, the saturated adsorption capacity increases considerably with the rise of pore size or the reduction of pore wall thickness, and the rise of pore size also leads to a dramatic increase in adsorption layer and a subsequent fall in ordering. However, when the pressure is less than 0.001P0, the monomolecular interaction energy and the isosteric heat are strengthened greatly with the addition of carboxyl and amino groups, while the threshold pressure shows an opposite change to the monomolecular interaction energy. In the meantime, the decrease of pore size or the increase of pore wall thickness will result in the same results. Findings in this paper can provide valuable insights into the microscopic mechanisms of the adsorption between activated carbon and VOCs.

Cobalt-Salen-Based Porous Ionic Polymer: The Role of Valence on Cooperative Conversion of CO2 to Cyclic Carbonate.

Cobalt-salen-based porous ionic polymers, which are composed of cobalt and halogen anions decorated on the framework, effectively catalyze the CO2 cycloaddition reaction of epoxides to cyclic carbonates under ambient conditions. The cooperative effect of bifunctional active sites of cobalt as the Lewis acidic site and the halogen anion as the nucleophile responds to the high catalytic performance. Moreover, density functional theory results indicate that the cobalt valence state and the corresponding coordination group influence the rate-determining step of the CO2 cycloaddition reaction and the nucleophilicity of halogen anions.

Confinement Phenomenon Effect on the CO2 Absorption Working Capacity in Ionic Liquids Immobilized into Porous Solid Supports.

In this work, the CO2 absorption working capacity and solubility in ionic liquids immobilized into porous solid materials (substrates) were studied both experimentally and theoretically. The CO2 absorption working capacity in the immobilized ionic liquids was measured experimentally. It was found that the CO2 absorption working capacity and solubility increased up to 10-fold compared to that in the bulk ionic liquids when the film thickness was nearly 2.5 nm in the [HMIm][NTf2] immobilized in the P25. Meanwhile, a new model was proposed to describe the Gibbs free energy of CO2 in the immobilized ionic liquids, and both macro- and microanalyses of the CO2 solubility in the confined ionic liquids were conducted. The theoretical investigations reveal that the substrate has a crucial effect on the gas solubility in the ionic liquid immobilized into the substrates, and the model performance was approved with a consideration of the substrate effect.

Wetting behavior of ionic liquid on mesoporous titanium dioxide surface by atomic force microscopy.

Ionic liquids based on 1-butyl-3-methylimidazolium hexafluoro-phosphate (ILs [Bmim][PF6]) has been employed to wet the mesoporous and dense titanium dioxide (TiO2) films. It has been found from atomic force microscopy (AFM) analysis that ILs [Bmim][PF6] can form a wetting phase on mesoporous TiO2 films, but nonwetting and sphere shaped droplets on dense films. AFM topography, phase images, and adhesion measurements suggest a remarkable dependence of wetting ILs [Bmim][PF6] films on the TiO2 porous geometry. On mesoporous TiO2 films, the adhesive force of ILs [Bmim][PF6] reaches at 40 nN, but only 4 nN on dense TiO2 films. The weak interacting ILs [Bmim][PF6] on dense TiO2 films forms rounded liquid spheres (contact angle as 40°), which helps to reduce friction locally but not on the whole surface. The stronger adhesive force on mesoporous TiO2 films makes ILs [Bmim][PF6] adhere to the surface tightly (contact angle as 5°), and this feature remains after five months. The stable spreading ILs [Bmim][PF6] films provide low friction coefficient (0.0025), large wetting areas, and short CO2 diffusion distance on the whole mesoporous TiO2 surface, avoiding the significant decelerating effect through equilibrium limitations to enable CO2 capture rate up to 1.6 and 10 times faster than that on dense TiO2 and pure ILs, respectively. And importantly, ILs wetted on mesoporous TiO2 shorten the time reaching to the maximum adsorption rate (2.8 min), faster than that on mesoporous TiO2 (6.1 min), and dense TiO2 (11.2 min). This work provides an important guidance for the improvement of the efficiency of CO2 capture, gas separation, and the lubrication of micro/nanoelectromechanical systems (M/NEMs).