During solvent extraction, amphiphilic extractants assist the transport of metal ions across the liquid-liquid interface between an aqueous ionic solution and an organic solvent. Investigations of the role of the interface in ion transport challenge our ability to probe fast molecular processes at liquid-liquid interfaces on nanometer-length scales. Recent development of a thermal switch for solvent extraction has addressed this challenge, which has led to the characterization by X-ray surface scattering of interfacial intermediate states in the extraction process. Here, we review and extend these earlier results. We find that trivalent rare earth ions, Y(III) and Er(III), combine with bis(hexadecyl) phosphoric acid (DHDP) extractants to form inverted bilayer structures at the interface; these appear to be condensed phases of small ion-extractant complexes. The stability of this unconventional interfacial structure is verified by molecular dynamics simulations. The ion-extractant complexes at the interface are an intermediate state in the extraction process, characterizing the moment at which ions have been transported across the aqueous-organic interface, but have not yet been dispersed in the organic phase. In contrast, divalent Sr(II) forms an ion-extractant complex with DHDP that leaves it exposed to the water phase; this result implies that a second process that transports Sr(II) across the interface has yet to be observed. Calculations demonstrate that the budding of reverse micelles formed from interfacial Sr(II) ion-extractant complexes could transport Sr(II) across the interface. Our results suggest a connection between the observed interfacial structures and the extraction mechanism, which ultimately affects the extraction selectivity and kinetics.

The interfacial behavior of a model solvent extraction liquid-liquid system, consisting of solutions of dihexadecyl phosphate (DHDP) in dodecane and SrCl2 in water, was studied to determine the structure of the interfacial ion-extractant complex and its variation with pH. Previous experiments on a similar extraction system with ErCl3 demonstrated that the kinetics of the extraction process could be greatly retarded by cooling through an adsorption transition, thus providing a method to immobilize ion-extractant complexes at the interface and further characterize them with X-ray interface-sensitive techniques. Here, we use this same method to study the SrCl2 system. X-ray reflectivity and fluorescence near total reflection measured the molecular-scale interfacial structure above and below the adsorption transition for a range of pH. Below the transition, DHDP molecules form a homogeneous monolayer at the interface with Sr(2+) coverage increasing from zero to saturation (one Sr(2+) per two DHDP) within a narrow range of pH. Experimental values of Sr(2+) interfacial density determined from fluorescence measurements are larger than those from reflectivity measurements. Although both techniques probe Sr(2+) bound to DHDP, only the fluorescence provides adequate sensitivity to Sr(2+) in the diffuse double layer. A Stern equation determines the Sr(2+) binding constant from the reflectivity measurements and the additional Sr(2+) measured in the diffuse double layer is accounted for by Gouy-Chapman theory. Above the transition temperature, a dilute concentration of DHDP-Sr complexes resides at the interface, even for temperatures far above the transition. A comparison is made of the structure of the interfacial ion-extractant complex for this divalent metal ion to recent results on trivalent Er(3+) metal ions, which provides insight into the role of metal ion charge on the structure of interfacial ion-extractant complexes, as well as implications for extraction of these two differently charged ions.

Experiments and computer simulations provide a new perspective that strong correlations of counterions with charged nanoparticles can influence the localization of nanoparticles at liquid-liquid interfaces and support the formation of voltage-tunable nanoparticle arrays. We show that ion condensation onto charged nanoparticles facilitates their transport from the aqueous-side of an interface between two immiscible electrolyte solutions to the organic-side, but contiguous to the interface. Counterion condensation onto the highly charged nanoparticles overcomes the electrostatic barrier presented by the low permittivity organic material, thus providing a mechanism to transport charged nanoparticles into organic phases with implications for the distribution of nanoparticles throughout the environment and within living organisms. After transport, the nanoparticles assemble into a two-dimensional (2D) nearly close-packed array on the organic side of the interface. Voltage-tunable counterion-mediated interactions between the nanoparticles are used to control the lattice spacing of the 2D array. Tunable nanoparticle arrays self-assembled at liquid interfaces are applicable to the development of electro-variable optical devices and active elements that control the physical and chemical properties of liquid interfaces on the nanoscale.

Previous X-ray scattering measurements demonstrated the formation of a voltage-tunable 2-dimensional lattice of nanoparticles situated at the liquid-liquid interface between two immiscible electrolyte solutions (Nano Letters 2014, 14, 6816−6822). The nanoparticles had Au cores coated with trimethylammonium terminated ligands and the ITIES consisted of NaCl in water and BTPPATPFB in 1,2-dichloroethane. Here, we present additional measurements on this system which illustrate a transition that occurs at more negative potentials. The transition represents a breakup of the 2D monolayer lattice into a disordered sub-monolayer of nanoparticles that coexists with small nanoparticle clusters in the vicinity of the interface. Grazing Incidence Small Angle X-ray Scattering (GISAXS) provides evidence for the breakup of the lattice and the appearance of clusters. X-ray reflectivity (XR) characterizes the relative location along the interfacial normal of the different types of nanoparticle assemblies.