Proton transfer across double layers- mechan- ism evaluation from isotopic effects
Hydrogen-tritium separation factors for determining mechanism of proton transfer across double layers
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Chelator‐Assisted Precipitation‐Based Separation of the Rare Earth Elements Neodymium and Dysprosium from Aqueous Solutions
The rare earth elements (REEs) are critical resources for many clean energy technologies, but are difficult to obtain in their elementally pure forms because of their nearly identical chemical properties. Here, an analogue of macropa, G-macropa, was synthesized and employed for an aqueous precipitation-based separation of Nd 3+ and Dy 3+ . G-macropa maintains the same thermodynamic preference for the large REEs as macropa, but shows smaller thermodynamic stability constants. Molecular dynamics studies demonstrate that the binding affinity differences of these chelators for Nd 3+ and Dy 3+ is a consequence of the presence or absence of an inner-sphere water molecule, which alters the donor strength of the macrocyclic ethers. Leveraging the small REE affinity of G-macropa, we demonstrate that within aqueous solutions of Nd 3+ , Dy 3+ , and G-macropa, the addition of HCO 3 − selectively precipitates Dy 2 (CO 3 ) 3 , leaving the Nd 3+ −G-macropa complex in solution. With this method, remarkably high separation factors of 841 and 741 are achieved for 50 : 50 and 75 : 25 mixtures. Further studies involving Nd 3+ :Dy 3+ ratios of 95 : 5 in authentic magnet waste also afford an efficient separation as well. Finally, G-macropa is recovered via crystallization with HCl and used for subsequent extractions, demonstrating its good recyclability.
Gao, Yangyang↗
The Cognition and Fine Motor Skills Test Batteries: Normative Data and Interdependencies
Space mission success and safety relies upon astronaut functional state. Since spaceflight stressors affect cognitive processing and fine motor skills, NASA requires that measures of performance of these things remain within clinically accepted values (NASA STD 3001). NASA is in the process of developing two test batteries for the assessment of crew cognitive and fine motor skills before, during and after spaceflight. Toward that goal, the current project collected normative scores in 91 “astronaut-like” military and civilian pilots. The Cognition Test Battery (CTB) contains ten sub-tests that measure a range of cognitive abilities. For five of the ten CTB sub-tests, we propose scores to improve the battery’s sensitivity. Among the ten sub-tests, response times were more highly correlated than accuracy scores. Principle component analysis of the correlations revealed that the first response time factor could explain over 40% of the total variance and appeared to represent the tendency of observers to try to respond more quickly. The first accuracy factor (explaining only 20%) gave a high weight to the higher level cognitive sub-tests and a negative weight to tasks associated with motor and lower level cognitive processing. The Fine Motor Skills (FMS) test battery contains four sub-tests (Tracking, Pointing, Tracing, Rotating) performed on an Apple iPad tablet computer. Principle component analysis on the sub-test response time correlations revealed that the first two factors accounted for ~80% of the variance in performance. The first component captured overall speed on all four of the sub-tests. The second factor separated the sub-tasks into two groups (Drag-Point vs Trace-Rotate). Previous work found the first group response times correlated with that of a standard peg board task, while those of the other group did not. Correlations were computed between the first FMS factor and the response time and accuracy scores from each CTB sub-task. Performing fine motor behaviors rapidly was significantly correlated with the ability to perform many of the CTB sub-tests rapidly. This ability cannot be simple motor speed since scores on the Psychomotor Vigilance Test (PVT) subtask did not correlate with the ability to perform the other tasks rapidly. Speed on fine motor skills correlated significantly with accuracy on the short-term-memory sub-test. We hypothesize that eye movements, which can be regarded as a fine motor skill, may explain this relationship.
cognition↗
Developing aqueous solubilizing agents as an alternative to solvent extraction
Here, advancing separations science is important for the entire field of chemistry. One partitioning technique that would benefit from improvement is solvent extraction. Despite its effective and widespread use, the method suffers from some problems: generation of flammable organic waste, lengthy process times, and safety concerns associated with contacting organic solvents with acidic aqueous solutions. We developed an alternative separation method inspired by solvent extraction that side-steps those issues. Toward this end, we identified that the functionality of an extractant (an agent used in solvent extraction to pull analytes from the aqueous phase into the organic phase) would change if it was modified for water solubility. In this alternative scenario, the extractant transforms into an “aqueous solubilizing agent.” We discovered that adding this aqueous solubilizing agent alongside a precipitating agent caused the contaminants to precipitate, but not the analyte. This separation concept was demonstrated within the bounds of one of the most difficult partitioning problems, separating minor actinides (Am 3+ ) from lanthanides (Ln 3+ ). We discovered that the (HSO 3 Ph) 4 BTP (aq) aqueous solubilizing agent prevented Am 3+ (aq) from precipitating with Ln 3+ (aq) when f-element precipitating agents (NaF (aq) or HF (aq) ) were added. This separation boasts impressive Am 3+ (aq) recovery yield (90 ± 2 %), near quantitative Ln 3+ (aq) removal, and high separation factors [>3000, Am 3+ (aq) vs. Nd 3+ (aq) ]. It seems likely – given the large number of candidate extractants that could be modified for aqueous solubility and the numerous combinations of existing solubilizing and precipitating agents – that this alternative approach could be used broadly in place of solvent extraction and solve other important separation problems.
(HSO3Ph)4BTP(aq)↗
Adsorption and Chromatographic Behavior of Dispersed Sodium Bismuthate Systems for the Separation of Americium from Curium
The selective partitioning of americium (Am) and curium (Cm) is integral for nuclear science areas such as the nuclear fuel cycle, stockpile stewardship, and isotope production but remains a long-standing radioanalytical challenge due to nearly identical chemical properties. Differences in redox chemistry can be exploited since Am can be oxidized to the hexavalent oxidation state. Sodium bismuthate (NaBiO 3 ) exhibits favorable oxidation and ion exchange characteristics conducive to a rapid and efficient Am/Cm chromatographic separation. Contact of nitric acid with NaBiO 3 was shown to significantly decrease the nitric acid concentration and solution volume. The adsorption, kinetic, and chromatographic behavior of Am and Cm in systems that disperse NaBiO3 in filter aids was evaluated. Further, dispersion of NaBiO 3 increased separation factors to over 100, with rapid kinetics achieved within 1 min of contact and sustained for at least 2 h. The adsorption capacity was more than doubled from 0.066 mequiv g –1 for solid NaBiO 3 alone to 0.149(6) and 0.156(9) meq g –1 when dispersed in Celite 545 and silica gel, respectively. Complete separation was achieved in all systems with ~100% recovery in the respective eluted fractions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Establishing Pb-203 production from electrodeposited Tl targets at Brookhaven National Laboratory
Background: Promising developments in Pb-212 radiopharmaceutical therapies have increased demand for Pb-203 diagnostic agents. Building on previous work from various isotope production facilities, this study optimized Pb-203 production from electrodeposited Tl targets at Brookhaven National Laboratory (BNL). The additional supply of Pb-203 may help meet growing preclinical and clinical demands. Results: Two Tl targets were irradiated at the Brookhaven Linac Isotope Producer facility with 30 ± 1 MeV protons, measured using previously published cross section data. Distribution coefficients for Pb Resin in acetate media were investigated for both Na + and K + cations, where potassium acetate was ~ 4 times more effective at stripping Pb from the Pb Resin. The Tl electrodeposition was optimized to deposit 350 mg of Tl (~ 60 mg/cm 2 ) on Au backing in under 6 h. The proposed separation process was completed in < 1.5 h and achieved > 98% and 92 ± 3% recovery of Tl and Pb, respectively, with an overall Tl-Pb separation factor of 6 × 10 5 . The experimentally measured half-life of Pb-203 was 52.4 ± 0.7 h, agreeing with 51.93 ± 0.02 h reported by the National Nuclear Data Center. The radioisotopic purity of the Pb fraction at 24 h post end of bombardment (EOB) from a 24 h irradiation was 66% Pb-203, 28% Pb-201, and 6% Pb-200. Following chemical separation, the Pb-203 produced in this work (21 MBq Pb-203 EOB) achieved apparent molar activities of 10 ± 5 and 0.9 ± 0.5 GBq/µmol for [ 203 Pb]Pb-DOTAM and [ 203 Pb]Pb-DO3A, respectively, decay corrected to EOB. Data derived from this work suggests BNL can produce > 10’s GBq Pb-203 with > 99% radiochemical and radioisotopic purity from Tl-205 for worldwide distribution. Conclusions: The production and separation of Pb-203 from natural Tl target material was successfully demonstrated at BNL. Existing methods were adapted and optimized for the facilities at BNL. Results from this work will guide future large-scale Pb-203 production opportunities at BNL for clinical applications.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Near-adjacent heavy lanthanide separation and sensing using dimerizing lanmodulins
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Biological and medical sciences↗
Engineering surface charges of nanofiltration membranes to maximize Li + /Mg 2+ separation properties
Polyamide-based nanofiltration (NF) membranes are attractive for Li + /Mg 2+ separation for lithium recovery from salt brine (containing mainly Mg 2+ ). However, Li + and Mg 2+ have similar hydration radii, resulting in a low separation factor (SF Li/Mg ). Herein, we demonstrate that SF Li/Mg can be significantly enhanced by optimizing the membrane surface positive charges. This results in an unexpected maximum SF Li/Mg at a solution pH slightly below its isoelectric point (IEP). Specifically, NF270 membrane was surface-grafted with 2-(methacryloyloxy)ethyltrimethylammonium chloride (META) or polyethylenimine (PEI) using bio-adhesive dopamine, forming a thin, stable, charged layer (20–40 nm) on the surface. The effects of solution pH and surface modification on the surface zeta potential (ZP) and single- and mixed-salt Li + /Mg 2+ separation properties are thoroughly investigated. For example, the META grafting increases the ZP from 9.2 to 16 mV and SF Li/Mg by 130 % from 35 to 80 at pH 4, superior to the state-of-the-art commercial NF membranes. Furthermore, this surface modification occurs at ≈22 °C in aqueous solutions and can be utilized to enhance commercial modules for practical applications.
Li+/Mg2+ separation↗
Vestibular and Non-vestibular Contributions to Eye Movements that Compensate for Head Rotations during Viewing of Near Targets
We studied horizontal eye movements induced by en-bloc yaw rotation, over a frequency range 0.2 - 2.8 Hz, in 10 normal human subjects as th ey monocularly viewed a target located at their near point of focus. We measured gain and phase relationships between eye-in-head velocity and head velocity when the near target was either earth-fixed or head-fixed. During viewing of the earth-fixed near target,median gain was 1.49 (range 1.24 - 1.87) at 0.2 Hz for the group of subjects, but decl ined at higher frequencies, so that at 2.8 Hz median gain was 1.08 (r ange 0.68 - 1.67). During viewing of the head-fixed near target, median gain was 0.03 (range 0.01 - 0.10) at 0.2 Hz for the group of subjec ts, but increased at higher frequencies, so that at 2.8 Hz median gai n was 0.71 (range 0.28 - 0.94). We estimated the vestibular contribution to these responses (vestibulo-ocular reflex gain, Gvor) by applyin g transient head perturbations (peak acceleration> 1,000 deg's(exp 2) ) during sinusoidal rotation under the two viewing conditions. Median Gvor, estimated < 70m after the onset of head perturbation, was 0.98 (range 0.39 - 1.42) while viewing the earth-fixed near target, and 0. 97 (range 0.37 - 1.33) while viewing the head-fixed near target. For the group of subjects, 9 out of 10 subjects showed no sigificant diff erence of Gvor between the two viewing conditions ( p > 0.053 ) at all test frequencies. Since Gvor accounted for only approximately 73% of the overall response gain during viewing of the earth-fixed target, we investigated the relative contributions of non-vestibular factors. When subjects viewed the earth-fixed target under strobe illumination , to eliminate retinal image slip information, the gain of compensato ry eye movements declined compared with viewing in ambient room light . During sum-of-sine head rotations, while viewing the earth-fixed target, to minimize contributions from predictive mechanisms, gain also declined Nonetheless, simple superposition of smooth-pursuit tracking of sinusoidal target motion could not fully account for the overall r esponse at higher frequencies, suggesting other non-vestibular contributions. During binocular viewing conditions when vergence angle was s ignificantly greater than monocular viewing (p < 0.001), this gain of compensatory eye movements did not show proportional change; indeed, gain could not be correlated with vergence angle during monocular or binocular viewing. We conclude that several separate factors contribute to generate eye rotations during sinusoidal yaw head rotations whi le viewing a near target; these include the VOR, visual-tracking eye movements that utilize retinal image motion, predictive eye movements and, possibly, other unidentified nonvestibular factors. For these experiments, vergence was not an important determinant of response gain .
Han, Yanning H.↗
Vestibular and Non-vestibular Contributions to Eye Movements that Compensate for Head Rotations during Viewing of Near Targets
We studied horizontal eye movements induced by en-bloc yaw rotation, over a frequency range 0.2 - 2.8 Hz, in 10 normal human subjects as they monocularly viewed a target located at their near point of focus. We measured gain and phase relationships between eye-in-head velocity and head velocity when the near target was either earth-fixed or head-fixed. During viewing of the earth-fixed near target, median gain was 1.49 (range 1.24 - 1.87) at 0.2 Hz for the group of subjects, but declined at higher frequencies, so that at 2.8 Hz median gain was 1.08 (range 0.68 - 1.67). During viewing of the head-fixed near target , median gain was 0.03 (range 0.01 - 0.10) at 0.2 Hz for the group of subjects, but increased at higher frequencies, so that at 2.8 Hz median gain was 0.71 (range 0.28 - 0.94). We estimated the vestibular contribution to these responses vestibulo-ocular reflex gain (Gvor) by applying transient head perturbations (peak acceleration> 1,000 deg/s(exp 2)) during sinusoidal rotation under the two viewing conditions. Median Gvor, estimated < 70ms after the onset of head perturbation, was 0.98 (range 0.39 - 1.42) while viewing the earth-fixed near target, and 0.97 (range 0.37 - 1.33) while viewing the head-fixed near target. For the group of subjects, 9 out of 10 subjects showed no significant difference of Gvor between the two viewing conditions ( p > 0.053 ) at all test frequencies. Since Gvor accounted for only -73% of the overall response gain during viewing of the earth-fixed target, we investigated the relative contributions of non-vestibular factors. When subjects viewed the earth-fixed target under strobe illumination, to eliminate retinal image slip information, the gain of compensatory eye movements declined compared with viewing in ambient room light. During sum-of-sine head rotations, while viewing the earth-fixed target, to Han et al./VOR during near-viewing minimize contributions from predictive mechanisms, gain also declined Nonetheless, simple superposition of smooth-pursuit tracking of sinusoidal target motion could not fully account for the overall response at higher frequencies, suggesting other nonvestibular contributions. During binocular viewing conditions when vergence angle was significantly greater than monocular viewing (p < 0.00l), the gain of compensatory eye movements did not show proportional change; indeed, gain could not be correlated with vergence angle during monocular or binocular viewing. We conclude that several separate factors contribute to generate eye rotations during sinusoidal yaw head rotations while viewing a near target; these include the VOR, visual-tracking eye movements that utilize retinal image motion, predictive eye movements and, possibly, other unidentified non-vestibular factors. For these experiments, vergence was not an important determinant of response gam.
Han, Yanning H.↗
Photonuclear production of 225 Ac from 226 Ra targets
Herein we report proof of principal production of 225 Ac via 226 Ra(γ , n) 225 Ra $\overset{^-β}{\rightarrow}$ 225 Ac and subsequent chemical separation via extraction chromatography using BDGA and Ln resins. Irradiation of 0.35 µg 226 Ra with 39 MeV bremsstrahlung end-point energy photons produced 225 Ra and 224 Ra at a rate of 754 and 2215 kBq/g 226 Ra/mA/h, respectively. The production rate of 225 Ac determined at its peak radioactivity was 335 kBq/g 226 Ra/mA/h. Radiochemically pure 225 Ac was isolated with a minimum separation factor of 125,000 for 225 Ac: 226 Ra. In conclusion, these results are promising and lay the foundation for future studies to scale-up production for preclinical quantities of high purity 225 Ac using the 226 Ra(γ , n) 225 Ra $\overset{^-β}{\rightarrow}$ 225 Ac approach.
38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi‐Purpose Polyamine Functionalization
2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10–30 nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm 2 and GO layer thicknesses of ≈500 nm are fabricated, and they exhibited a stable dye water permeance of 75 L m −2 h −1 bar −1 , rejection of >99.5% for Direct red and Congo red, and Na 2 SO 4 /dye separation factor of 300–500, superior to state-of-the-art commercial membranes. Furthermore, the versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.
amine functionalization↗
TALSPEAK-based separation of the trivalent actinides from rare earth elements using LN resin
The separation of 241 Am, 244 Cm and 249 Cf from rare earth elements using LN resin and lactate buffer solutions with diethylenetriaminepentaacetic acid is described with numerous columns studies. The elutions are based on TALSPEAK liquid–liquid extraction chemistry, and provide high yield (> 90%), rapid, simple separations of the trivalent actinides from the lanthanides, which is often challenging due to similarities in chemical behavior among the trivalent f-block elements. Further, all three actinides can be separated from rare earth elements, including from massless fission product samples and samples with small amounts (~ 1–5 mg) of stable lanthanides. Separations with no detectable overlap between the actinide and lanthanide elutions is possible with massless samples, and in samples with mass high separation factors can be achieved (Am/Eu: 171; Am/La: 10 6 ).
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Vacuum-assisted carbon molecular sieve membrane reactor for non-oxidative ethane dehydrogenation
Non-oxidative ethane dehydrogenation (EDH) is equilibrium-limited and endothermic. Selective hydrogen removal using a gas-permeable membrane within the EDH reaction zone can overcome the thermodynamic equilibrium, enabling higher ethane conversions. Employing vacuum as the permeation driving force, rather than a sweep gas, enhances the industrial viability of membrane reactors by eliminating additional post-reaction separation units. This study presents a membrane reactor that integrates H 2 -permeable carbon molecular sieve (CMS) hollow fiber membranes embedded in a fixed bed of cobalt in a dealuminated beta zeolite (Co@DeAl-BEA) catalyst, utilizing a vacuum to remove hydrogen efficiently. The CMS membrane exhibits high hydrogen permeance and an excellent H 2 /C 2 H 6 separation factor. The membrane reactor significantly enhanced the ethane conversion under reaction conditions comparable to those reported in the literature. A Langmuir-Hinshelwood kinetic rate expression was developed and incorporated into a one-dimensional steady-state reactor model. The experimentally validated model indicates that increasing the number of hollow fibers improves ethane conversion, although ethane loss to the permeate limits the benefit. The contact area between the catalyst and the membrane limits the reactor performance more than the catalytic throughput. Furthermore, we find that the location of the catalyst packing relative to the hollow fiber membranes influences ethane loss and conversion. Higher reactor pressures and inlet ethane flow rates improve space-time yield at the expense of lower ethane conversion. Increasing reactor temperature or packing length promotes both performance metrics. The EDH membrane reactor demonstrated durability over 200 h of continuous operation, maintaining record-low deactivation rates and high ethylene selectivity. Protocols for catalyst regeneration were developed.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Solar-powered self-descaling seesaw extractor for lithium production from seawater
The low Li + concentration and the abundance of competing ions limit the efficiency of lithium extraction from seawater. Here, in this work, we report a solar-powered seesaw extractor (SPSE) to boost Li + adsorption while minimizing scaling caused by competing ions during photothermal evaporation. The SPSE features a sandwich architecture, with a hydrophilic adsorbent layer placed between two hydrophobic photothermal layers. The seesaw configuration enables Li + to be elevated and concentrated through evaporation to overcome sluggish adsorption kinetics, while the associated salt scaling is removed by the seesawing motion. As a demonstration, we assembled 60 SPSEs into a 3 × 20 array that achieved a 15.5-fold increase in local Li + concentration and a 69.1% improvement in Li + uptake over 120 h, with a Li + /Na + separation factor exceeding 370,000.
localized enrichment↗
Electrochemical Recovery of Rare-Earth Elements from Coal Fly Ash Using Ionic Liquids as both Extractant and Electrolyte
Rare-earth elements (REEs) are critical for medical technologies, electronics, and clean energy. Coal fly ash (CFA), a byproduct of coal combustion, offers a promising alternative REE source. However, efficient extraction and separation of REEs from CFA remain challenging due to the complex composition of CFA. This study introduces a sustainable method for REE recovery using a recyclable ionic liquid, betainium bis(trifluoromethylsulfonyl)imide ([Hbet]- [Tf 2 N]), which serves both as the extractant from CFA and as the electrolyte in electrodeposition. In the first stage, [Hbet][Tf 2 N] preferentially extracts REEs from CFA through leaching. In the second stage, the REE-enriched ionic liquid undergoes electrochemical deposition using amperometry techniques, where REEs are reduced and deposited onto the electrode. The deposition experiments were conducted from −0.5 to −2.0 V vs a Pt quasireference electrode in a three-electrode setup comprising titanium as the working electrode and platinum as both the reference and counter electrodes. Varying the applied potential enabled potential-dependent preferential REE deposition. At −0.5 V, neodymium (Nd) showed preferential recovery, reaching 25% with a separation factor of 37 over other REEs. In contrast, applying a more negative potential increased overall deposition, yielding ∼50% Nd recovery and 10−20% recovery for the remaining REEs. After recovery, the ionic liquid was regenerated and reused for a subsequent electrochemical recovery cycle. Overall, this study demonstrates a feasible approach for REE recovery from CFA waste, with potential to enhance resource utilization within the REE supply chain.
coal fly ash↗
Enhancing f -Element Separations with ADAAM-EH: The Impact of Phase Modifiers and a DGA Aqueous Complexant
Recent investigations have used a 2-ethylhexyl diamide amine (ADAAM-EH) for Am/Cm separations in combination with N,N,N ',N '-tetraethyldiglycolamide as an aqueous complexant to achieve an unprecedented separation factor of 41. The aim of this research effort is to understand the speciation of trivalent lanthanide (Ln) and actinide (An) ions in the organic phase of an ADAAM-EH extraction system, both with and without phase modifiers (PM) (1-octanol and tri-n-butyl phosphate (TBP)). Leveraging spectroscopic techniques in combination with distribution ratio measurements provides an understanding of organic phase f-element ligand complexation. In the absence of PM, Ln is extracted in a stoichiometric 1:1 [M(ADAAM-EH) 1 (NO 3 ) x (H 2 O) 1 ](NO 3 ) 3-x complex. The addition of 1-octanol at 20 vol % results in multiple species present. One of the species is the same as the no PM case, and the other species results in an increased -OH coordination to the inner sphere, potentially displacing some NO 3 . In the case of TBP, increasing concentration results in additional red-shifted bands in the UV-visible spectra, suggesting the complexation of additional ligands of either ADAAM-EH or TBP. Finally, the new system knowledge obtained by and spectroscopic experiments will provide benchmarking information for computational studies of the inner- and outer-sphere coordination environments of f-element cations and insights into ADAAM-EH adduct formation with PM, like 1-octanol and TBP.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Developing Lanthanide-Nitrate Cluster Chemistry toward Rare Earth Separations
Nitrate-decorated hexamers with a [Ln 6 (μ 6 -O)(μ 3 –OH) 8 ] 8+ core have been reported for nearly every lanthanide ion and are used as precursors for the assembly of functional metal–organic frameworks. Yet, few studies have examined the correlation between the solution and solid-state species, and the formation of mixed-metal clusters. Toward this end, a series of homo- and heterometal lanthanide nitrate hexamers was prepared via pH adjustment of aqueous lanthanide nitrate solutions. Examination of the homometallic europium solutions using Small Angle X-ray Scattering and nESI-MS showed that lower order complexes dominate lanthanide speciation in nitrate media. Yet, powder X-ray diffraction data of the precipitated phase confirmed the formation of [Ln 6 (μ 6 -O)(μ 3 -OH) 8 (NO 3 ) 6 (H 2 O) 12 ]·2(NO 3 )·n(H 2 O), Ln 6 , for Ln = Eu and Tb. For heterometal systems, analysis of the solid-state product by ICP–MS showed the selective incorporation of the heavier rare earths into Ln 6 . Selectivity was quantified by calculating an average separation factor, which is defined as the ratio of recovery factors of both metals. Further examination of the luminescence behavior of mixed metal [Tb 6–x Eu x (μ 6 -O)(μ 3 -OH) 8 (NO 3 ) 6 (H 2 O) 12 ]·2(NO 3 )·n(H 2 O), with x = 1.1–3.6, showed that the relative intensities of the peaks at 489 nm (terbium, 5 D 4 → 7 F 6 ) and 690 nm (europium, 5 D 0 → 7 F 4 ) trend with the percent incorporation of europium and terbium into the cluster.
anions↗