Ross J. Ellis

Selective Extraction and Transport of the [PtCl6]2− Anion through Outer-Sphere Coordination Chemistry

A series of tripodal receptors designed to recognise the outer coordination sphere of the hexachlorometallate anion [PtCl(6)](2-), and thus show selectivity for ion-pair formation over chloride binding, has been synthesised and characterised. The tripodal ligands contain urea, amido or sulfonamido hydrogen-bond donors, which are aligned to bind to the regions of greatest electron density along the faces and edges of the octahedral anion. The ligand structure incorporates a protonatable bridgehead nitrogen centre that provides a positive charge to ensure the solubility of a neutral 2:1 [LH](+)/[PtCl(6)](2-) complex in water-immiscible solvents. The extraction of [PtCl(6)](2-) from acidic chloride solutions was evaluated by using a pH-swing mechanism to control the loading and stripping of the metallate anion. The ligands L(1)-L(3), L(5)-L(9), L(11)-L(13) and L(15) showed extremely high loading (up to 95% in some cases) and high selectivity for [PtCl(6)](2-) over chloride ions (present in a 60-fold excess) compared with trioctylamine, a model Alamine reagent, which, under identical conditions, only extracted 10% of the Pt(IV) anions. Generally, extraction was observed to be greater for urea-containing ligands than their amido analogues, and a quantitative recovery of platinum from feed solutions was achieved. The formation of neutral ([LH](+))(2)[PtCl(6)](2-) packages in organic media is supported by single-crystal X-ray structure determinations of [(L(2)H)(2)PtCl(6)] x 2 CH(3)CN, [(L(8)H)(2)PtCl(6)(MeOH)(2)], [(L(12)H)(2)PtCl(6)] x 2 CH(3)CN and [(L(14)H)(2)PtCl(6)], which confirm the presence of significant hydrogen bonding between the anion and urea or amido moieties of the protonated ligand and the anion. The structure of [(L(1)H)(H(3)O)PtCl(6)] x C(6)H(6) x CH(3)CN shows hydrogen bonding of a H(3)O(+) cation to the receptor and confirms that other stoichiometries are also possible, indicating that speciation in solution may be more complex.

A SAXS Study of Aggregation in the Synergistic TBP–HDBP Solvent Extraction System

The macroscopic phase behaviors of a solvent system containing two extractants, tri-n-butyl phosphate (TBP) and di-n-butyl phosphoric acid (HDBP) in n-dodecane, were investigated through use of liquid-liquid extraction and small-angle X-ray scattering (SAXS) experiments. Five organic solutions, each containing a total extractant concentration (TBP + HDBP) of 1 M in varying molar ratios (0, 0.25, 0.5, 0.75, and 1.0 [TBP]:[TBP + HDBP]), were contacted with 0.2 M HNO3 aqueous solutions without and with dysprosium(III) at a concentration of 10(-4) M. An enhancement of the extraction of Dy(3+)--due to effects of synergism arising from the binary combination of extractants--was observed. SAXS data were collected for all solution compositions from 0 to 1 mol-fraction end ratios of TBP after contact with the acidic aqueous solutions both in the absence and presence of Dy as well as for the organic phases before aqueous contact. In the precontacted solutions, no notable changes in the SAXS data were observed upon combining the extractants so that the scattering intensity (I) measured at zero angle (Q = 0 Å(-1))--parameter I(0)--the experimental radius of gyration (R(g)), and the maximum linear extent (MLE) of the extractant aggregates were arithmetic averages of the two end members, 1 M HDBP, on the one hand, and 1 M TBP, on the other. In contrast, after contact with the aqueous phases with and without Dy(3+), a significant reorganization occurs with larger aggregates apparent in the extractant mixtures and smaller in the two end member solutions. In particular, the maximum values of the metrical parameters (I(0), R(g), and MLE) correlate with the apparent optimal synergistic extraction mole ratio of 0.25. The SAXS data were further analyzed using the recently developed generalized indirect Fourier transformation (GIFT) method to provide pair-distance distribution functions with real-space information on aggregate morphology. Before aqueous contact, the organic phases show a systematically varying response from globular-like reverse micelles in the case of 1 M TBP to rod-shaped architectures in the case of 1 M HDBP. After aqueous contact, the aggregate morphologies of the mixed extractant systems are not simple linear combinations of those for the two end members. Rather, they have larger and more elongated structures, showing sharp discontinuities in the metrics of the aggregate entities that are coincident with the synergistic extraction mixture for Dy(3+). The results in this initial study suggest a supramolecular, micellization aspect to synergism that remains underexplored and warrants further investigation, especially as it concerns the contemporary relevance to decades-old process chemistry and practices for high throughput separations systems.

How Hydrogen Bonds Affect the Growth of Reverse Micelles around Coordinating Metal Ions

Extensive research on hydrogen bonds (H-bonds) have illustrated their critical role in various biological, chemical and physical processes. Given that existing studies are predominantly performed in aqueous conditions, how H-bonds affect both the structure and function of aggregates in organic phase is poorly understood. Herein, we investigate the role of H-bonds on the hierarchical structure of an aggregating amphiphile-oil solution containing a coordinating metal complex by means of atomistic molecular dynamics simulations and X-ray techniques. For the first time, we show that H-bonds not only stabilize the metal complex in the hydrophobic environment by coordinating between the Eu(NO3)3 outer-sphere and aggregating amphiphiles, but also affect the growth of such reverse micellar aggregates. The formation of swollen, elongated reverse micelles elevates the extraction of metal ions with increased H-bonds under acidic condition. These new insights into H-bonds are of broad interest to nanosynthesis and biological applications, in addition to metal ion separations.

Mesoscopic aspects of phase transitions in a solvent extraction system.

In liquid-liquid extraction, organic phase splitting arises when high concentrations of polar solutes (acids/metal ions) are extracted. Herein, we investigate the mesoscopic roots that underpin phase splitting in alkane phases containing mixed amphiphiles, of contemporary interest in solvent extraction separation systems, by extracting various oxoacids. The oxoacids exhibited individual macroscopic (extractive and physical) behaviors, inducing phase splitting into heavy and light domains under markedly different conditions. Using small-angle X-ray scattering (SAXS) data analyzed using the generalized indirect Fourier transform (GIFT) method, we showed that, in all cases, acid extraction drove the self-assembly of reverse micelles into rods. These grew with increased acid extraction until reaching a critical length of 20 nm, at which point interactions produced interconnected cylinders or lamellar sheets that prelude phase splitting into heavy and light domains. In all cases, the heavy phase contained the same surfactant ratio-TBP (tri-n-butyl phosphate) and CMPO (octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide)-even though the concentrations of acid, water, and amphiphiles were markedly different. The remarkable similarities in structure and amphiphile stoichiometries underpinning phase splitting across the macroscopically different acid extraction series allude to the mesoscopic roots of organic phase behavior in solvent extraction. Our studies show that the structures underpinning phase splitting in solvent extraction systems are more complex than previously thought and are reminiscent of phase transitions in soft matter.

Molecular Origins of Mesoscale Ordering in a Metalloamphiphile Phase

Controlling the assembly of soft and deformable molecular aggregates into mesoscale structures is essential for understanding and developing a broad range of processes including rare earth extraction and cleaning of water, as well as for developing materials with unique properties. By combined synchrotron small- and wide-angle X-ray scattering with large-scale atomistic molecular dynamics simulations we analyze here a metalloamphiphile–oil solution that organizes on multiple length scales. The molecules associate into aggregates, and aggregates flocculate into meso-ordered phases. Our study demonstrates that dipolar interactions, centered on the amphiphile headgroup, bridge ionic aggregate cores and drive aggregate flocculation. By identifying specific intermolecular interactions that drive mesoscale ordering in solution, we bridge two different length scales that are classically addressed separately. Our results highlight the importance of individual intermolecular interactions in driving mesoscale ordering.

Revisiting the Solution Structure of Ceric Ammonium Nitrate

Ceric ammonium nitrate (CAN) is a single-electron-transfer reagent with unparalleled utility in organic synthesis, and has emerged as a vital feedstock in diverse chemical industries. Most applications use CAN in solution where it is assigned a monomeric [Ce(IV) (NO3 )6 ](2-) structure; an assumption traced to half-century old studies. Using synchrotron X-rays and Raman spectroscopy we challenge this tradition, converging instead on an oxo-bridged dinuclear complex, even in strong nitric acid. Thus, one equivalent of CAN is recast as a two-electron-transfer reagent and a redox-activated superbase, raising questions regarding the origins of its reactivity with organic molecules and giving new fundamental insight into the stability of polynuclear complexes of tetravalent ions.

Amide-Functionalized Aliphatic Amine Extractants for Co(II) and Zn(II) Recovery from Acidic Chloride Media

Abstract A novel series of amido-functionalized amine reagents has been developed, which are designed for the extraction of anionic metal chloride complexes according to the following equation The new reagents were investigated for Zn(II), Co(II), and Fe(III) recovery in order to establish conditions under which the selectivity for base metals over Fe(III) could be achieved. They were found to be much stronger than the aliphatic amine benchmark extractant tris(2-ethylhexyl) amine (TEHA), giving good Zn(II) and Co(II) recovery from solutions with high enough pH to precipitate Fe(III). The new reagents also gave improved Zn(II) extraction from solutions with moderate to low chloride concentration so that the selectivity for Zn(II) over Fe(III) might be achieved at [Cl] < 1 M.

A Simple Primary Amide for the Selective Recovery of Gold from Secondary Resources

Waste electrical and electronic equipment (WEEE) such as mobile phones contains a plethora of metals of which gold is by far the most valuable. Herein a simple primary amide is described that achieves the selective separation of gold from a mixture of metals typically found in mobile phones by extraction into toluene from an aqueous HCl solution; unlike current processes, reverse phase transfer is achieved simply using water. Phase transfer occurs by dynamic assembly of protonated and neutral amides with [AuCl4 ](-) ions through hydrogen bonding in the organic phase, as shown by EXAFS, mass spectrometry measurements, and computational calculations, and supported by distribution coefficient analysis. The fundamental chemical understanding gained herein should be integral to the development of metal-recovery processes, in particular through the use of dynamic assembly processes to build complexity from simplicity.

“Straining” to Separate the Rare Earths: How the Lanthanide Contraction Impacts Chelation by Diglycolamide Ligands

The subtle energetic differences underpinning adjacent lanthanide discrimination are explored with diglycolamide ligands. Our approach converges liquid-liquid extraction experiments with solution-phase X-ray absorption spectroscopy (XAS) and density functional theory (DFT) simulations, spanning the lanthanide series. The homoleptic [(DGA)3Ln]3+ complex was confirmed in the organic extractive solution by XAS, and this was modeled using DFT. An interplay between steric strain and coordination energies apparently gives rise to a nonlinear trend in discriminatory lanthanide ion complexation across the series. Our results highlight the importance of optimizing chelate molecular geometry to account for both coordination interactions and strain energies when designing new ligands for efficient adjacent lanthanide separation for rare-earth refining.

Synergistic Extraction of Dysprosium and Aggregate Formation in Solvent Extraction Systems Combining TBP and HDBP

During treatment of nuclear fuel in the Plutonium/URanium EXtraction (PUREX) process, the extractant tri-n-butyl phosphate (TBP) is known to degrade to dibutylphosphoric acid (HDBP), which increases the extraction of metal ions, thereby inhibiting their stripping from the organic phase. To better understand this phenomenon, we investigated how mixtures of TBP and HDBP influenced the extraction of metal, nitric acid, and water, and correlated the results to aggregated structures in the organic phase. The mole ratios of TBP-HDBP mixtures had a non-linear effect on the extraction of Dy3+ and water from 0.2 M HNO3, indicating synergism. In 2 M HNO3, the TBP:HDBP mole ratio had a more linear relation to Dy3+ and water extraction, so the synergistic effect was less pronounced than in the low acid system. The extraction of nitric acid showed no synergistic effect and follows closely what would be expected in a system using TBP only. The small-angle X-ray scattering (SAXS) data of the 0.2 M acid system showed maximum contrast at a TBP:HDBP mole ratio of 0.25, so that the synergistic mixture is also the most aggregated at 0.2 M acid. The 2 M acid system also showed that the mixed system is more aggregated than the end members, although this does not result in peak extraction. Previous studies of synergistic extraction of metal cations explain the enhanced extraction by increased dehydration of the metal ion. Although our data do not rule out the formation of mixed complexes according to the classical mechanism of synergism, our evidence of increased water extraction and aggregate formation in systems combining TBP and HDBP are complementary to the metal-centric dehydration aspects of the process. The findings in this study give insights into the complex chemistry of solvent extraction, providing a possible link between formation of aggregates in the organic phase and synergistic extraction.