Binyang Hou

Tuning ion correlations at an electrified soft interface

Ion distributions play a central role in various settings—from biology, where they mediate the electrostatic interactions between charged biomolecules in solution, to energy storage devices, where they influence the charging properties of supercapacitors. These distributions are determined by interactions dictated by the chemical properties of the ions and their environment as well as the long-range nature of the electrostatic force. Recent theoretical and computational studies have explored the role of correlations between ions, which have been suggested to underlie a number of counterintuitive results, such as like-charge attraction. However, the interdependency between ion correlations and other interactions that ions experience in solution complicates the connection between physical models of ion correlations and the experimental investigation of ion distributions. We exploit the properties of the liquid/liquid interface to vary the coupling strength of ion–ion correlations from weak to strong while monitoring their influence on ion distributions at the nanometer scale with X-ray reflectivity and the macroscopic scale with interfacial tension measurements. These data are in agreement with the predictions of a parameter-free density functional theory that includes ion–ion correlations and ion–solvent interactions over the entire range of experimentally tunable correlation coupling strengths (from 0.8 to 3.7). This study provides evidence for a sharply defined electrical double layer for large coupling strengths in contrast to the diffuse distributions predicted by mean field theory, thereby confirming a common prediction of many ion correlation models. The reported findings represent a significant advance in elucidating the nature and role of ion correlations in charged soft matter.

Communications: Monovalent ion condensation at the electrified liquid/liquid interface

X-ray reflectivity studies demonstrate the condensation of a monovalent ion at the electrified interface between electrolyte solutions of water and 1,2-dichloroethane. Predictions of the ion distributions by standard Poisson-Boltzmann (Gouy-Chapman) theory are inconsistent with these data at higher applied interfacial electric potentials. Calculations from a Poisson-Boltzmann equation that incorporates a nonmonotonic ion-specific potential of mean force are in good agreement with the data.

Observation of a Rare Earth Ion–Extractant Complex Arrested at the Oil–Water Interface During Solvent Extraction

Selective extraction of metal ions from a complex aqueous mixture into an organic phase is used to separate toxic or radioactive metals from polluted environments and nuclear waste, as well as to produce industrially relevant metals, such as rare earth ions. Selectivity arises from the choice of an extractant amphiphile, dissolved in the organic phase, which interacts preferentially with the target metal ion. The extractant-mediated process of ion transport from an aqueous to an organic phase takes place at the aqueous-organic interface; nevertheless, little is known about the molecular mechanism of this process despite its importance. Although state-of-the-art X-ray scattering is uniquely capable of probing molecular ordering at a liquid-liquid interface with subnanometer spatial resolution, utilizing this capability to investigate interfacial dynamical processes of short temporal duration remains a challenge. We show that a temperature-driven adsorption transition can be used to turn the extraction on and off by controlling adsorption and desorption of extractants at the oil-water interface. Lowering the temperature through this transition immobilizes a supramolecular ion-extractant complex at the interface during the extraction of rare earth erbium ions. Under the conditions of these experiments, the ion-extractant complexes condense into a two-dimensional inverted bilayer, which is characterized on the molecular scale with synchrotron X-ray reflectivity and fluorescence measurements. Raising the temperature above the transition leads to Er ion extraction as a result of desorption of ion-extractant complexes from the interface into the bulk organic phase. XAFS measurements of the ion-extractant complexes in the bulk organic phase demonstrate that they are similar to the interfacial complexes.

Ion Distributions at the Water/1,2-Dichloroethane Interface: Potential of Mean Force Approach to Analyzing X-ray Reflectivity and Interfacial Tension Measurements

We present X-ray reflectivity and interfacial tension measurements of the electrified liquid/liquid interface between two immiscible electrolyte solutions for the purpose of understanding the dependence of interfacial ion distributions on the applied electric potential difference across the interface. The aqueous phase contains alkali-metal chlorides, including LiCl, NaCl, RbCl, or CsCl, and the organic phase is a 1,2-dichloroethane solution of bis(triphenylphosphor anylidene) ammonium tetrakis(pentafluorophenyl)borate (BTPPATPFB). Selected data for a subset of electric potential differences are analyzed to determine the potentials of mean force for Li(+), Rb(+), Cs(+), BTPPA(+), and TPFB(-). These potentials of mean force are then used to analyze both X-ray reflectivity and interfacial tension data measured over a wide range of electric potential differences. Comparison of X-ray reflectivity data for strongly hydrated alkali-metal ions (Li(+) and Na(+)), for which ion pairing to TPFB(-) ions across the interface is not expected, to data for weakly hydrated alkali-metal ions (Rb(+) and Cs(+)) indicates that the Gibbs energy of adsorption due to ion pairing at the interface must be small (<1 k(B)T per ion pair) for both the CsCl and RbCl samples. This paper demonstrates the applicability of the Poisson-Boltzmann potential of mean force approach to the analysis of X-ray reflectivity measurements that probe the nanoscale ion distribution and the consequences of these underlying distributions for thermodynamic studies, such as interfacial tension measurements, that yield quantities related to the integrated ion distribution.

X-ray fluorescence from a model liquid/liquid solvent extraction system

X-ray fluorescence near total reflection (XFNTR) is measured from the liquid/liquid interface between dodecane and an ErCl3 aqueous solution by monitoring L shell Er emission lines. A custom sample cell is used to minimize absorption of the fluorescence x-rays that pass through dodecane on their way to the detector. The Er3+ concentration near the interface is related to the fluorescence intensity by a scale factor that is extracted by fitting the incident-angle dependent Er Lα emission line intensities for different ErCl3 bulk concentrations. As an application, we present the use of XFNTR to monitor the growth of interfacial crud in a model solvent extraction system consisting of an interface between a dodecane solution of bis(2-ethylhexyl) phosphate (HDEHP) and an ErCl3 aqueous solution.

Electric Field Effect on Phospholipid Monolayers at an Aqueous–Organic Liquid–Liquid Interface

The electric potential difference across cell membranes, known as the membrane potential, plays an important role in the activation of many biological processes. To investigate the effect of the membrane potential on the molecular ordering of lipids within a biomimetic membrane, a self-assembled monolayer of 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine (SOPC) lipids at an electrified 1,2-dichloroethane/water interface is studied with X-ray reflectivity and interfacial tension. Measurements over a range of electric potential differences, -150 to +130 mV, that encompass the range of typical biomembrane potentials demonstrate a nearly constant and stable structure whose lipid interfacial density is comparable to that found in other biomimetic membrane systems. Measurements at higher positive potentials, up to 330 mV, illustrate a monotonic decrease in the lipid interfacial density and accompanying variations in the interfacial configuration of the lipid. Molecular dynamics simulations, designed to mimic the experimental conditions, show that the measured changes in lipid configuration are due primarily to the variation in area per lipid with increasing applied electric field. Rotation of the SOPC dipole moment by the torque from the applied electric field appears to be negligible, except at the highest measured potentials. The simulations confirm in atomistic detail the measured potential-dependent characteristics of SOPC monolayers. Our hybrid study sheds light on phospholipid monolayer stability under different membrane potentials, which is important for understanding membrane processes. This study also illustrates the use of X-ray surface scattering to probe the ordering of surfactant monolayers at an electrified aqueous-organic liquid-liquid interface.

The Hydration Structure at Yttria-Stabilized Cubic Zirconia (110)-Water Interface with Sub-Ångström Resolution

The interfacial hydration structure of yttria-stabilized cubic zirconia (110) surface in contact with water was determined with ~0.5 Å resolution by high-resolution X-ray reflectivity measurement. The terminal layer shows a reduced electron density compared to the following substrate lattice layers, which indicates there are additional defects generated by metal depletion as well as intrinsic oxygen vacancies, both of which are apparently filled by water species. Above this top surface layer, two additional adsorbed layers are observed forming a characteristic interfacial hydration structure. The first adsorbed layer shows abnormally high density as pure water and likely includes metal species, whereas the second layer consists of pure water. The observed interfacial hydration structure seems responsible for local equilibration of the defective surface in water and eventually regulating the long-term degradation processes. The multitude of water interactions with the zirconia surface results in the complex but highly ordered interfacial structure constituting the reaction front.

Effect of defects on reaction of NiO surface with Pb-contained solution

In order to understand the role of defects in chemical reactions, we used two types of samples, which are molecular beam epitaxy (MBE) grown NiO(001) film on Mg(001) substrate as the defect free NiO prototype and NiO grown on Ni(110) single crystal as the one with defects. In-situ observations for oxide-liquid interfacial structure and surface morphology were performed for both samples in water and Pb-contained solution using high-resolution X-ray reflectivity and atomic force microscopy. For the MBE grown NiO, no significant changes were detected in the high-resolution X-ray reflectivity data with monotonic increase in roughness. Meanwhile, in the case of native grown NiO on Ni(110), significant changes in both the morphology and atomistic structure at the interface were observed when immersed in water and Pb-contained solution. Our results provide simple and direct experimental evidence of the role of the defects in chemical reaction of oxide surfaces with both water and Pb-contained solution.

Topological Dirac line nodes and superconductivity coexist in SnSe at high pressure

We report on the discovery of a pressure-induced topological and superconducting phase of SnSe, a material which attracts much attention recently due to its superior thermoelectric properties. In situ high-pressure electrical transport and synchrotron x-ray diffraction measurements show that the superconductivity emerges along with the formation of a CsCl-type structural phase of SnSe above around 27 GPa, with a maximum critical temperature of 3.2 K at 39 GPa. Based on ab initio calculations, this CsCl-type SnSe is predicted to be a Dirac line-node (DLN) semimetal in the absence of spin-orbit coupling, whose DLN states are protected by the coexistence of time-reversal and inversion symmetries. These results make CsCl-type SnSe an interesting model platform with simple crystal symmetry to study the interplay of topological physics and superconductivity.