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At least 631 records · Page 35

Electrochemical generation of useful chemical species from lunar materials

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Sammells, Anthony F.↗

The electrochemical generation of useful chemical species from lunar materials

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Sammells, Anthony F.↗

Activated transport in AMTEC electrodes

Transport of alkali, metal atoms through porous cathodes of alkali metal thermal-to-electric converter (AMTEC) cells is responsible for significant reducible losses in the electrical performance of these cells. Experimental evidence for activated transport of metal atoms at grain surfaces and boundaries within some AMTEC electrodes has been derived from temperature dependent studies as well as from analysis of the detailed frequency dependence of ac impedance results for other electrodes, including thin, mature molybdenum electrodes which exhibit transport dominated by free molecular flow of sodium gas at low frequencies or dc conditions. Activated surface transport will almost always exist in parallel with free molecular flow transport, and the process of alkali atom adsorption/desorption from the electrode surface will invariably be part of the transport process, and possibly a dominant part in some cases. The temperature dependence of the diffusion coefficient of the alkali metal through the electrode in several cases provides an activation energy and preexponential, but at least two activated processes may be operative, and the activation parameters should be expected to depend on the alkali metal activity gradient that the electrode experiences. In the case of Pt/W/Mn electrodes operated for 2500 hours, limiting currents varied with electrode thickness, and the activation parameters could be assigned primarily to the surface/grain boundary diffusion process.

Williams, R. M.↗

The Au Cathode in the System Li2CO3-CO2-CO at 800 to 900 C

Gold is one of several metals being evaluated at NASA Lewis Research Center as positive electrode catalysts for an alkali metal/molten alkali metal carbonate/carbon dioxide electrochemical cell. Such a cell is proposed for CO2-rich planetary atmospheres such as those of Mars and Venus. Its application could be as a primary power supply, as a secondary power supply recharged either 'chemically' by replenishment of the alkali metal or electrochemically from a central station power source, or as a converter of carbon dioxide to oxygen via a complete electrochemical cycle. For the work being reported, lithium was assumed to be the alkali metal of choice for the negative electrode of the cell, and therefore molten lithium carbonate was the electrolyte used in the Au electrode experiments. Cathodic linear sweep voltammetry (LSV) was the primary analytical technique for evaluating the performance of the Au cathode. interest comprised the cell temperature and the total pressure and composition of the reactant gas. In the absence of operational difficulties, the effect of bubbling the reactant gas through the melt was also determined. On the basis of the variation of electrode performance with changes in these parameters, inferences have been made concerning the electrochemical and chemical processes at and near the electrode. The results of post-test micrographic analyses of the Au cathode are also presented. An attempt is then made to project from the experimental results to some relevant conclusions pertaining to a gold cathode in a practical alkali metal - carbon dioxide cell.

Hagedorn, Norman H.↗

Isomolybdate conversion coatings

A conversion coating solution and process forms a stable and corrosion-resistant layer on metal substrates or layers or, more preferably, on a boehmite layer or other base conversion coating. The conversion coating process involves contacting the substrate, layer or coating with an aqueous alkali metal isomolybdate solution in order to convert the surface of the substrate, layer or coating to a stable conversion coating. The aqueous alkali metal molybdates are selected from sodium molybdate (Na.sub.2 MoO.sub.4), lithium molybdate (Li.sub.2 MoO.sub.4), potassium molybdate (K.sub.2 MoO.sub.4), or combinations thereof, with the most preferred alkali metal molybdate being sodium molybdate. The concentration of alkali metal molybdates in the solution is preferably less than 5% by weight. In addition to the alkali metal molybdates, the conversion coating solution may include alkaline metal passivators selected from lithium nitrate (LiNO.sub.3), sodium nitrate (NaNO.sub.3), ammonia nitrate (NH.sub.4 NO.sub.3), and combinations thereof; lithium chloride, potassium hexafluorozirconate (K.sub.2 ZrF.sub.6) or potassium hexafluorotitanate (K.sub.2 TiF.sub.6).

Minevski, Zoran↗

Investigation of Magmatic Activities on Early Mars Using Igneous Mineral Chemistry in Gale Crater, Mars

One objective of rover missions is exploring the geological context of the surroundings. Over the years, igneous petrology and sedimentology have been disconnected, the first investigating magmatic processes and volcanic activities, and the second seeking environmental conditions in the past and assessing the habitability of the planet. Although different, one is related to the other: igneous rocks are altered and broken down, leading to the formation of sedimentary rocks, which can in turn be used to back out the nature of their magmatic source. The Curiosity rover that landed in the 3.7 Gyr old impact crater Gale is traveling through sedimentary rocks. About fifty float rocks have been observed, and several of them with ambiguous texture and composition have been classified as igneous or sedimentary depending on studies such as Jake_M. The composition of several unambiguous igneous rocks has been analyzed [4- 6] but their heterogeneity at a larger instrumental (measurement size < 2 cm) scale prevents the measurement of a bulk composition as performed on Earth. An original approach avoiding these two last issues is to consider igneous mineral chemistry analyzed within igneous and sedimentary rocks to assess magmatic processes that could have formed them. Most Curiosity data are used to explore ancient environmental conditions, and a significant number of compositional analyses are under-explored for constraining magmatic activities. We will present how we can make use of sedimentary data for investigating igneous processes in the vicinity of Gale crater. Geological Context: We focus on the first 750 martian days, corresponding to measurements in a coherent lacustrine sedimentary unit called Bradbury, because all sedimentary rocks were sourced from the same watershed and appear to have a consistent source with minimal alteration [2-3]. Igneous detrital minerals including feldspar and pyroxene, are observed in sedimentary rocks. Monte Carlo models showed that minimal cation loss is observed based on the composition of all Bradbury rocks, implying negligible weathering [3]. Although clay minerals are detected in few rocks [7], chemical compositions of rocks can be explained by a mixture of primary igneous minerals [3]. Variation of composition within Bradbury rocks can be explained by mineral sorting and one distinct source component. While a common magmatic source is suggested, Bradbury sediments likely come from several volcanic eruptions from a single magmatic chamber [9- 10]. The occurrence of alkali minerals like sanidine and K-rich rocks throughout Bradbury supports the presence of a potassic component, likely trachytic, while plagioclase and a mafic composition suggest a basaltic component [8-9]. Instruments: Mineral chemistry can be estimated by three instruments onboard Curiosity. The CheMin instrument enables detection of mineral assemblages using X-ray diffraction (XRD). Using Rietveld refinement, each mineral is identified according to their 1D XRD pattern [11]. Note that distinction between pyroxene minerals is challenging with the CheMin instrument due to overlapping peaks on XRD patterns and low angular resolution of the instrument [12]. Then, using least square regression and optimization algorithms based on unit-cell parameters, mineral chemistry has been estimated by [11]. Plagioclase composition has been estimated using the NaAlSi3O8- CaAl2Si2O8 system and alkali feldspar is based on the NaAlSi3O8-KAlSi3O8 system (stars in Fig.1). Two mudstone samples (John Klein and Cumberland) and one sandstone sample (Windjana) were analyzed by CheMin at Yellowknife Bay and Kimberley, respectively. Figure 1. Ternary diagrams of feldspars (top) and pyroxene (bottom) quadrilateral. Stars correspond to CheMin composition and the gray patches to ChemCam composition. The colored dots are the composition of feldspar and pyroxene that crystallized during fractional crystallization at FMQ+1 of a melt extracted at distinct melting degree during the adiabatic ascent of a primitive mantle composition, without any water (left panels) and with 0.5 wt.% of water (right panels) at distinct pressure. The ChemCam instrument enables the analysis of the chemical compositions of rocks at hundreds of micrometer scale (350-550 μm) using laser induced breakdown spectroscopy (LIBS), which may provide the composition of minerals when they are larger than the beam spot (>550 μm) [13]. Within >5000 LIBS points, we performed a typical stoichiometric filtering allowing us to distinguish 56 feldspar and 10 pyroxene mineral compositions (grey patches in Fig. 1). Finally, the Alpha Particle X-ray Spectrometer (APXS) analyzes the composition of rocks with a 1.6 cm diameter spot size. Monte Carlo mass balance modeling allowed [3] to decipher a feldspar range varying between An30 and An40 (Fig. 1). Discussion: Although there could be a more complex history and other ways to form the whole compositional range of igneous minerals analyzed within the Bradbury formation, we are presenting here simple magmatic pathways commonly occurring on Earth using the thermodynamical softwares pMELTS and rhyoliteMELTS [14]. The objective is to find reasonable igneous processes that produce minerals that parallel the compositions of feldspar and pyroxene analyzed by the Curiosity rover. As commonly observed for mid-ocean ridge basalts, the adiabatic ascent of a primitive mantle composition [15] partially melting at 2 GPa has been modeled, followed by the extraction of a liquid at distinct degrees of partial melting, which undergoes fractional crystallization at an oxygen fugacity +1 log unit above the fayalite-magnetite-quartz (FMQ) buffer within the crust (0.02-0.4 GPa) with H2O = 0- 0.5 wt. %. These latter conditions correspond to those recorded within igneous clasts from the Noachian martian breccia NWA 7034 and paired and within Gale igneous rocks (colored dots in Fig. 1) [16-17]. To check the reliability of these 2-step models, we also tested fractional crystallization at similar conditions (FMQ+1; P=0.02-0.4 GPa; H2O = 0-0.5 wt. %) of starting compositions corresponding to that of magmas with distinct melting degrees obtained from isobaric experiments at 2 GPa [18]. Mineral compositions obtained from both models are similar. As shown on Fig. 1, the whole range of observed feldspar compositions cannot be reproduced by fractionation of one magma only. Indeed, while alkali feldspar and Na-plagioclase likely crystallized from fractional crystallization of a low-degree melt (here <15%), plagioclase and pyroxene can only be formed by fractional crystallization of a higher degree melt (here >19%). The corresponding liquid descent lines are broadly in agreement with compositions estimated by ChemCam corresponding to float igneous rocks (Fig. 2) [4-6]. Figure 2. Silica versus alkali content. Lines show the liquid lines of descent from magmas with distinct degrees of melting. Gray patches represents the composition of Gale igneous rocks [4-6]. Trachytic to rhyolitic magmas crystallize alkali feldspar, and andesite to dacite magmas likely form plagioclase. Therefore, at least two starting magmas at distinct melting degrees, which could easily come from a single mantle source, are necessary to explain the whole compositional range of feldspar and pyroxene analyzed within Bradbury rocks. Conclusion: Because rocks from the Bradbury formation are likely originating from the same magmatic source with minimal weathering as supported by several studies using different approaches, igneous mineral chemistry analyzed by CheMin and ChemCam allows us to back out reasonable magmatic pathways that could have crystallized them. Fractional crystallization of at least two starting magmas originating from distinct melting degrees of a single mantle source can explain the whole range of feldspar and pyroxene composition. Both alkaline and sub-alkaline liquids can be produced, with compositions corresponding to those of the igneous rocks analyzed by ChemCam within the Bradbury formation, highlighting the complexity of Mars magmatism.

Payre, V.↗

Advanced Thin Film Core Technology: CIGS Final Technical Report (FTR)

Cu(In,Ga)Se 2 (CIGS) thin-film photovoltaics are a high-efficiency and reliable technology. This project completed research in two important areas and was designed to work collaboratively with industrial partners. Task 1: Alkali Science focused on alkali post-deposition treatments (PDT). PDTs have been instrumental in the dramatic voltage improvements that have moved CIGS device efficiencies from 20% to 23.35% [1]. Based on a survey of CIGS companies at the beginning of the project, the single biggest breakthrough for the CIGS community would be a mechanistic understanding of the role of alkalis in the material system. Significant accomplishments of Task 1: Alkali Science: 1) KF post-deposition treatments were shown to improve lifetime, open-circuit voltage (VOC), and efficiency of industrial partner samples, even when done as a later step, separate from the original CIGS deposition. 2) KF boosted efficiency when incorporated at the end of the third stage of NREL CIGS growth. 3) XPS characterization of CIGS surfaces with and without PDTs led to a proposed mechanism whereby K drives structural transformation at 350 degrees C that is locked in at room temperature even after K is rinsed away. 4) Published recipes for KF and RbF PDTs. Literature to date did not provide enough detail to quickly reproduce experimental results. 5) Identified most important parameters (RbF cell temperature and lamp setpoint temperature) and set boundaries for successful RbF PDTs. The purpose of Task 2: Cell-level Reliability was to overcome the largest challenges to investor confidence and long product lifetime in CIGS-based photovoltaic products: metastability, shading-induced hot spots, and potential-induced degradation (PID). Key findings were made in each of these areas by studying CIGS reliability at the cell level: 1) Published NREL's cell-level reliability testing procedures along with challenges that were encountered while developing them. These were also distributed to the community through an MRS conference presentation. 2) Decreased metastability by adding a CdS hole-injection layer between the CIGS and Zn(O,S) in the device stack. It also improved device performance. Materials other than CdS can be used for the same purpose. 3) Reduced front-glass PID by replacing soda-lime glass with low-Na borosilicate glass. 4) Found that PID depends on leakage current and light/electrical bias. This will help labs avoid test-specific degradation. 5) Discovered that CIGS can suffer from two different types of PID with different mechanisms. Front is slower and leads to shunting ZnO. Back is faster and degrades the p-n junction. 6) Holding cells at open circuit slows PID compared to short circuit. This affects testing protocols for glass/glass modules.

14 SOLAR ENERGY↗

Advances in Studies of Electrode Kinetics and Mass Transport in AMTEC Cells (abstract)

Previous work reported from JPL has included characterization of electrode kinetics and alkali atom transport from electrodes including Mo, W, WRh(sub x), WPt(sub x)(Mn), in sodium AMTEC cells and vapor exposure cells, and Mo in potassium vapor exposure cells. These studies were generally performed in cells with small area electrodes (about 1 to 5 cm(sup 2)), and device geometry had little effect on transport. Alkali diffusion coefficients through these electrodes have been characterized, and approximate surface diffusion coefficients derived in cases of activated transport. A basic model of electrode kinetic at the alkali metal vapor/porous metal electrode/alkali beta'-alumina solid electrolyte three phase boundary has been proposed which accounts for electrochemical reaction rates with a collision frequency near the three phase boundary and tunneling from the porous electrode partially covered with adsorbed alkali metal atoms. The small electrode effect in AMTEC cells has been discussed in several papers, but quantitative investigations have described only the overall effect and the important contribution of electrolyte resistance. The quantitative characterization of transport losses in cells with large area electrodes has been limited to simulations of large area electrode effects, or characterization of transport losses from large area electrodes with significant longitudinal temperature gradients. This paper describes new investigations of electrochemical kinetics and transport, particularily with WPt(sub 3.5) electrodes, including the influence of electrode size on the mass transport loss in the AMTEC cell. These electrodes possess excellent sodium transport properties making verification of device limitations on transport much more readily attained.

electrode kinetics alkali atom transport transport↗

Advances in Studies of Electrode Kinetics and Mass Transport in AMTEC Cells

Previous work reported from JPL has included characterization of electrode kinetics and alkali atom transport from electrodes including Mo, W, WRh x (Mn), in sodium AMTEC cells and vapor exposure cells; and Mo in potassium vapor exposure cells. These studies were generally performed in cells with small area electrodes (about 1 to 5 cm 2 ), and device geometry had little effect on transport. Alkali metal diffusion coefficients through these electrodes have been characterized, and approximate surface diffusion coefficients were derived in cases of activated transport. A basic model of electrode kinetics and transport at the alkali metal vapor/pourous metal electrode/alkali beta"-alumina solid electrolyte (BASE) three phase boundary has been proposed which accounts for electrochemical reaction rates with a collision frequency near the three phase boundary and tunneling from the porous electrode partially covered with adsorbed alkali metal atoms. The small electrode effect in AMTEC cells has been discussed in several papers, but quantitative investigations have described only the overall effect and the important contribution of electrolyte resistance. The quantitative characterization of transport losses in cells with large area electrodes has been limited to simulations of large area electrode effects, or characterization of transport losses from large area electrodes with significant longitudinal temperature gradients. This paper describes new investigations of electrochemical kinetics and transport, with four 14.4 cm 2 WPt 3.5 electrodes, including the influence of electrode size on the mass transport loss in the AMTEC cell. These electrodes exhibit very slow sintering, as well as excellent sodium transport properties, making them attractive candidates for AMTEC power conversion use. However, the facile sodium transport in WPt 3.5 electrodes makes characterization of the transport process difficult.

electrode↗

Stabilizing Anionic Redox Chemistry in a Mn-Based Layered Oxide Cathode Constructed by Li-Deficient Pristine State

Li-rich cathode materials are of significant interest for coupling anionic redox with cationic redox chemistry to achieve high-energy-density batteries. However, lattice oxygen loss and derived structure distortion would induce serious capacity loss and voltage decay, further hindering its practical application. Herein, a novel Li-rich cathode material, O3-type Li 0.6 [Li 0.2 Mn 0.8 ]O 2 , is developed with the pristine state displaying both a Li excess in the transition metal layer and a deficiency in the alkali metal layer. Benefiting from stable structure evolution and Li migration processes, not only can high reversible capacity (≈329 mAh g -1 ) be harvested but also irreversible/reversible anionic/cationic redox reactions are comprehensively assigned via the combination of in/ex situ spectroscopies. Furthermore, irreversible lattice oxygen loss and structure distortion are effectively restrained, resulting in long-term cycle stability (capacity drop of 0.045% per cycle, 500 cycles). Altogether, tuning the Li state in the alkali metal layer presents a promising way for modification of high-capacity Li-rich cathode candidates.

anionic redox reactions↗

The physiochemical alteration of flax fibers structuring components after different scouring and bleaching treatments

Scouring and bleaching are essential steps in flax yarn production; however, in many cases, these treatments have relatively low selectivity on non-cellulosic polysaccharides (NCPs) and lignin. Herein, the specific chemical properties of flax fibers through a variety of scouring and/or bleaching procedures are reviewed to understand their correlations with the mechanical and morphological characteristics. The hydrolysis behaviors of hemicellulose and lignin are different from those of cellulose during chlorine-alkali-oxygen (Cl-AO), enzyme-alkali-oxygen (EAO), and alkali-oxygen (AO) treatments, while the structural hemicellulose polysaccharides fractions were not affected by acid pretreatment followed by alkali scouring (AA) treatment. It was found that the unbleached AA treatment improved scouring efficiency to the greatest extent by decreasing 73.3 % of hemicellulose content and 59.8 % of lignin content compared to the untreated flax fibers and obtained the highest tensile strength (6.58 cN/dtex) and elongation (3.73 %). Delignification was more crucial on fiber tenacity and fineness than hemicellulose removal (R 2 = 0.71, 0.79 vs R 2 = 0.46, 0.61). Within the hemicellulose fractions, a corresponding beneficial relationship between the xylan (XYL) composition and flax fiber properties is presented. The correlation of GM and GGM contents in hemicellulose with flax fiber length was significant with R 2 value 0.97 and 0.99, respectively. This work provides insight into the hydrolysis behavior of hemicellulose and a basis for developing scouring and/or bleaching models that can predict fiber properties.

60 APPLIED LIFE SCIENCES↗

Pectin-associated mannans and xylans play distinct roles in cell-cell adhesion in pine and poplar wood

Wood particles of pine required longer treatments of acidic chlorite and dilute alkali to achieve similar proportions of cell separation as of poplar. Chemical extraction and enzymatic digestion studies indicated that rhamnogalacturonan-I (RG-I), mannan and xylan contribute to cell-cell adhesion in pine wood. Mannan associated with lignin in an acidic chlorite fraction and with xylan in a dilute alkali fraction. RG-I and xylan were extracted in both chlorite and dilute alkali in poplar. Scanning electron microscopy and a probe diffusion study using Fluorescence Recovery After Photobleaching showed that lignin, RG-I and mannan initiated cell separation at cell corners and dilute alkali extraction of xylan was required for complete cell separation in pine. Cell-cell separation increased enzymatic saccharification within 24 h by 2-fold in poplar and 3.4-fold in pine. Finally, our results inform a strategy to reduce particle size in woody biomass and provide insights into different molecular bases of cell-cell adhesion.

59 BASIC BIOLOGICAL SCIENCES↗

Exploring the Origin of Anionic Redox Activity in Super Li-Rich Iron Oxide-Based High-Energy-Density Cathode Materials

Super alkali-rich materials (alkali:transition metal ratio of ≥2:1), such as Li 5 FeO 4 , exhibit the potential to realize anionic redox upon deep delithiation. Li 5 FeO 4 was shown to undergo reversible cycling between Li 4 FeO 3.5 and Li 3 FeO 3.5 with combined cation/anion redox, a remarkable capacity of 189 mAh/g, and no O 2 release. However, the impact of phase transformations on the reaction thermodynamics and the correlation between the structural changes and reaction reversibility remain unclear. In this study, we use first-principles calculations to examine the delithiation and (re)lithiation reactions of Li 5 FeO 4 . We show that the experimentally observed charge and discharge processes go through non-equilibrium pathways. Upon delithiation, the compound undergoes a phase transformation from Li 5 FeO 4 , with tetrahedrally coordinated (T d ) Fe ions, to a delithiated disordered rocksalt structure, with octahedral (O h ) Fe ions. Fe-ion migration has an asymmetric kinetic barrier that makes T d → O h migration facile, whereas the reverse process has a much larger barrier, explaining the difficulties in reaction reversibility. We further elucidate the transition metal and O redox sequences during the charge cycle and identify the complex electrochemistry associated with the dual participation of cationic redox (Fe 3+ /Fe 4+ ) and anionic redox (O 2– /O – /O o ). Armed with this knowledge, we conduct high-throughput screening of known alkali-rich transition metal oxides by evaluating their potential to enable reversible anionic redox, with multiple candidates proposed for further experimental trials. Furthermore, our work provides a useful guide for the further development of super alkali-rich anionic-redox-active electrodes for high-energy-density batteries.

25 ENERGY STORAGE↗

Structures and Magnetic Properties of K 2 Pd 4 U 6 S 17 , K 2 Pt 4 U 6 S 17 , Rb 2 Pt 4 U 6 S 17 , and Cs 2 Pt 4 U 6 S 17 Synthesized Using the Boron–Chalcogen Mixture Method

A series of A 2 M 4 U 6 S 17 (A = Alkali metal, M = Pd or Pt) compounds, specifically K 2 Pd 4 U 6 S 17 , K 2 Pt 4 U 6 S 17 , Rb 2 Pt 4 U 6 S 17 , and Cs 2 Pt 4 U 6 S 17 , were synthesized using the combined Boron-Chalcogen Mixture (BCM) and molten flux crystal growth methods. The formation of the Rb- and Cs- containing analogues resulted from the in-situ alkali polysulfide flux formation formed from the alkali carbonates. The successful synthesis of single crystals of the title compounds allowed for their structural characterization by single crystal X-ray diffraction. The structure determination revealed disorder of the alkali cations in Rb 2 Pt 4 U 6 S 17 , and Cs 2 Pt 4 U 6 S 17 , while the potassium cations in K 2 Pd 4 U 6 S 17 and K 2 Pt 4 U 6 S 17 were fully ordered. Here, magnetic measurements were performed on samples of K 2 Pt 4 U 6 S 17 , Rb 2 Pt 4 U 6 S 17 , and Cs 2 Pt 4 U 6 S 17 that contained small amounts of paramagnetic β-US 2 and diamagnetic PtS. Antiferromagnetic order is observed at T N = 9.1 K for K 2 Pt 4 U 6 S 17 . No long-range magnetic order was observed for Rb 2 Pt 4 U 6 S 17 and Cs 2 Pt 4 U 6 S 17 . Uranium moments of 2.5, 2.6, and 2.6 μB were measured for K 2 Pt 4 U 6 S 17 , Rb 2 Pt 4 U 6 S 17 , and Cs 2 Pt 4 U 6 S 17 , respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cations Enhance Hydride Transfer to Noncatalytic Metals in Concentrated Alkaline Electrolytes

Alkali metal cations are known to influence the kinetics of the hydrogen evolution reaction (HER), acting as either promoters or inhibitors to the rate-determining step depending on the metal surface, local pH, and cation concentration. Despite the importance of concentrated electrolytes for commercial electrochemical cells, the impact of cations on the HER in concentrated alkaline environments (>1 M) and in mixed cation systems remains poorly understood. Here, this study quantifies the HER kinetics at polycrystalline metal surfaces (Pt, Au, Cu, and Fe) and the equilibrium solvation environment in pure and mixed alkali metal hydroxide electrolytes at concentrations up to 3.0 M. Kinetic analyses of Au, Cu, and Fe revealed a positive cation-concentration-effect that was primarily driven by changes to the charge transfer coefficient. Multinuclear NMR spectroscopy examined the solvation of H 2 O/OH – species and the alkali cations as a function of (mixed) alkali cation concentration(s), and demonstrated rapid exchange between solvent, hydroxide, and solvated cations. Together, these findings support models where HER kinetics on noncatalytic metal surfaces in strongly alkaline conditions are primarily governed by the average polarization and polarizability of the metal/solution interface and that increasing cation activity continues to increase the transfer coefficient at metal-hydroxide concentrations up to 3.0 M. Electrolytes and additives which can outcompete weakly hydrated cations and disrupt the interfacial water structure are expected to suppress parasitic HER at electrodes for energy storage and electroplating.

Cations↗

Design strategies for nonaqueous multivalent-ion and monovalent-ion battery anodes

The inability of current battery technologies to keep up with the performance requirements of industry is pushing forward developments in electrochemistry. Specifically, the battery's negative electrode, the anode, presents many unique chemical, physical and engineering challenges. Lithium-based battery technologies have dominated the past decade, but concerns about the limited supply of lithium in the Earth's crust have led researchers to look towards alternative metal-ion technologies. Furthermore, various alkali metals (such as sodium and potassium) and alkali earth metals (such as magnesium and calcium) have attracted significant research interest. In this Review, we analyse these technologies in a coherent manner, addressing the problems of each type of anode, rather than those of specific types of metal-ion batteries. Covering direct metal plating and stripping, intercalation-based, alloy-based and conversion-reaction-based anode technologies, this analysis will offer the reader a comprehensive understanding of the behaviour of different metal-ion anodes and of what can be learned by transferring knowledge between these different systems. Increasing demand for energy-storage systems will inevitably stress the Earth's lithium supply; thus, the research focus is shifting towards other alkali and alkali earth metals. In summary, this Review compares and connects strategies to enable different multivalent and monovalent metal-ion battery anodes, including metal anodes and intercalation-based, alloy-based and conversion-reaction-based anodes.

36 MATERIALS SCIENCE↗

Flux crystal growth of uranium(v) containing oxyfluoride perovskites

The novel phases Rb 4 NaU 3 O 12-x F x (1), K 4 NaU 3 O 12-x F x (2), and Rb 2.1 K 1.9 KU 3 O 12-x F x (3) were synthesized by molten flux methods using mixed alkali fluoride melts. The oxyfluorides crystallize in the cubic space group Im[3 with combining macron]m with a lattice parameters of 8.7472(2) Å, 8.6264(2) Å, and 8.8390(3) Å, respectively. All three structures crystallize in a cubic perovskite structure, ABO 3 (A 4 BB' 3 O 12 ), where the A site is fully occupied by an alkali cation, and the B site is shared by the remaining smaller alkali cation and uranium in an ordered fashion such that the alkali cation on the B site is surrounded by square uranyl bipyramids. The structures were characterized by single crystal X-ray diffraction, energy dispersive spectroscopy, X-ray absorption near edge structure spectroscopy, X-ray photoelectron spectroscopy, magnetic susceptibility measurements, DFT calculations, thermogravimetric analysis, and UV-vis spectroscopy, all of which support the presence of U(V) in the three new materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Isotherm Model for Moisture-Controlled CO 2 Sorption

Moisture-controlled sorption of CO 2 , the basis for moisture-swing CO 2 capture from air, is a novel phenomenon observed in strong-base anion exchange materials. Prior research has shown that Langmuir isotherms provide an approximate fit to moisture-controlled CO 2 sorption isotherm data. However, this fit still lacks a governing equation derived from an analytic model. As such, in this paper we derive an analytic form for an isotherm equation from a bottom-up approach, starting with a fundamental theory for an alkali liquid. In the range of interest relevant to CO 2 capture from air, an isotherm equation for an alkali liquid reduces to a simple analytic form with a single parameter, $K_{\text{eq}}$. In the limit $K_{\text{eq}} \gg 1$, a 2nd order approximation simplifies to a Langmuir isotherm that, however, deviates from experimental data. The isotherm theory for an alkali liquid has been generalized to a strong-base anion exchange material. In a strong-base anion exchange material, water concentration inside a sorbent, [H 2 O], is not large enough to be regarded as constant, which allows us to extend $K_{\text{eq}}$ to $K_{\text{eq(AEM)eff}} = K_{\text{eq(AEM)}} \times$ [H 2 O]$^{–n}$ according to the law of mass action. The final isotherm formula has been validated by experimental data from the literature. For a moisture-controlled CO 2 sorbent, $K_{\text{eq(AEM)eff}}$ varies significantly with moisture content of the sorbent. Depending on moisture level, the observed $K_{\text{eq(AEM)eff}}$ in a specific sorbent ranges from a few times to a few thousand times the value of $K_{\text{eq}}$ of a 2 mol L –1 alkali liquid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗