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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,477 records · Page 82
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Capacitive Deionization for the Extraction and Recovery of Butyrate

Separation processes underpin chemical manufacturing, energy and fuel production, resource recovery, and water purification. Capacitive deionization (CDI) is an electrochemical separation technique based on electrosorption of charged species from an aqueous solution. This work reports the development and application of CDI for the extraction and recovery of butyrate, a carboxylate anion that is key to bioenergy production, among other applications. Electrosorption of sodium butyrate was evaluated using a bench-scale CDI system with activated carbon cloth electrodes. Applying an external potential (1.2 V) enhanced the adsorption capacity of activated carbon for butyrate by 250%. Reversible electrosorption was also demonstrated by extracting and recovering butyrate at 1.2 and 0 V, respectively. Performance metrics including butyrate adsorption and desorption capacities, adsorption and desorption rates, charge efficiency, energy consumption, and recovery are reported. Furthermore, this study also investigates the long-term operational stability of the system by cycling the cell more than 1000 times using 1.2 and 0 V for charging and discharging, respectively. Subsequent physicochemical characterization indicates increased oxygen content (from similar to 2% to >8%), decreased specific surface area (by similar to 20%), and decreased pore volume (by similar to 20%), attributed to carbon oxidation. Overall, this work informs the design of CDI for organic anion separation and recovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Synthesis of Carbohydrates from Methanol Using Electrochemical Partial Oxidation over Palladium with the Integrated Formose Reaction

Electrochemically derived multicarbon products are a golden target for valorization of captured carbon dioxide due to the potential of turning a waste product into useful commodity chemicals with renewable energy sources. As a tantalizing approach toward their synthesis, the formose reaction utilizes catalytic condensation of formaldehyde to generate carbohydrates. Furthermore, while a sustainable approach to artificial carbohydrate production through electrochemical generation of formaldehyde is desirable, to date, it has not been fully realized. Here, we study the electrocatalytic conversion of methanol to formaldehyde on palladium with faradaic efficiency of over 90% at 0.9 V vs Ag/AgCl and with the partial current density of nearly 3 mA cm -2 at 1.6 V vs Ag/AgCl. We observe the concurrent generation of palladium oxides as a consequence of the high overpotentials employed, which may partially explain the higher selectivity toward the partial oxidation product. Moreover, we demonstrate that formaldehyde produced electrochemically from methanol is feasible for formose reactions without the need for further purification, achieving 21-28% carbon conversion to carbohydrates. This process, therefore, represents a potential avenue for the electrochemical generation of formaldehyde and its utilization in generating multicarbon products inaccessible by other electrocatalytic means.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Sustainable and Energy-Efficient Production of Rare-Earth Metals via Chloride-Based Molten Salt Electrolysis

Neodymium metal is a critical component of rare earth magnets, essential for electric vehicles and the green energy transition, but its production has severe environmental impacts across its mining, separation, purification, and metal electrowinning steps. Specifically, conventional neodymium electrowinning in oxyfluoride molten salts using a consumable graphite anode generates greenhouse gases, e.g., carbon dioxide and perfluorocarbon (PFC). We propose an alternative chloride-based molten salt electrolysis process utilizing a novel dimensionally stable anode (DSA). Our process lowers the specific electrical energy consumption compared to the state of the art, while producing reusable chlorine gas and eliminating direct CO 2 and PFC emissions. Chloride-based molten salt electrolysis of NdCl 3 (1.65 M) added to a LiCl–KCl eutectic (45:55 wt %), while using a RuO 2 -coated DSA enables high Coulombic efficiency (>80%), low specific energy consumption (2.3 kWh/kg-Nd), and excellent electrowon Nd product purity (>97 wt %). Life cycle analysis, excluding the common input feedstock (Nd 2 O 3 ), shows that the global warming potential for the proposed chloride-based electrolysis approach is 5 kg CO 2 equivalent, compared to 9–16 kg CO 2 equivalent for the conventional process, representing a 44–69% reduction in CO 2 emissions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Recovery of p -Hydroxybenzoic Acid from Cu-Catalyzed Alkaline Hydrogen Peroxide Pretreatment of Hybrid Poplar

p-Hydroxybenzoic acid (pHBA) is present in some hardwood biomass feedstocks as an ester attached to the polymeric lignin subunits. Here, we report the isolation and recovery of pHBA from alkaline liquor waste streams obtained from fractionation of hybrid poplar using the “Cu-AHP process”. This process features two stages: alkaline pre-extraction (AP) of the biomass and copper-catalyzed alkaline hydrogen peroxide pretreatment. On a biomass scale of 100 g, 0.5 g of pHBA with a purity of 96% was obtained after decolorization and crystallization. The scalability of the purification process was demonstrated by using liquor obtained from the first-stage AP with 900 g of poplar biomass to afford 3.5 g of crystalline pHBA with 97% purity. Altogether, these results show that pHBA may be isolated and purified from waste streams generated in the two-stage Cu-AHP process without any alteration of the process conditions or impact on carbohydrate and lignin fractionation.

09 BIOMASS FUELS↗
DOE OSTI2024

Oxidative Catalytic Fractionation of Lignocellulosic Biomass Using a Co-N-P-C Catalyst and One-Step Isolation of Aromatic Monomers via Centrifugal Partition Chromatography

Methods for catalytic fractionation of biomass provide a means to convert lignin directly into monomers while generating a high-quality cellulosic stream, contrasting conventional biomass pretreatment strategies that prioritize the cellulosic fraction. Here, a nonprecious-metal Co-N-P-C catalyst is identified for aerobic oxidative catalytic fractionation (OCF) of poplar feedstock in dimethyl carbonate that achieves significantly higher yields of aromatic monomers (24 wt %) relative to those obtained with a recently reported Co-N-C catalyst in acetone solvent (15 wt %). Mechanistic studies indicate that the acidic properties of the catalyst contribute to its improved performance by promoting extraction of lignin from insoluble polysaccharides. This OCF process is complemented by the development of a new centrifugal partition chromatography (CPC) method that supports isolation of all five major aromatic monomers (syringic acid, syringaldehyde, vanillic acid, vanillin, and para-hydroxybenzoic acid) in a single liquid–liquid extraction purification step. Furthermore, this OCF/CPC sequence has important implications for future lignin valorization efforts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrochemical Cycling of Liquid Organic Hydrogen Carriers as a Sustainable Approach for Hydrogen Storage and Transportation

Hydrogen (H 2 ), as a high-energy-density molecule, offers a clean solution to carry energy. However, the high diffusivity and low volumetric density of H 2 pose a challenge for long-term storage and transportation. Liquid organic hydrogen carriers (LOHCs) have been suggested as a strategic way to store and transport hydrogen in stable molecules. More so, electrochemical LOHC cycling renders an opportunity to utilize renewable energy for hydrogen storage and transportation toward the goal of eliminating carbon emissions. In this Perspective, examples of electrochemical reactions of organic molecules and their suitability for LOHC couples are examined. A comparative carbon footprint assessment of electrochemical LOHC cycling processes against thermochemical and hybrid LOHC cycling processes was performed. The electrochemical LOHC cycling process had the lowest relative carbon footprint only when highly concentrated LOHCs were used as the feed or when purification of the LOHC product was not required. The carbon footprint in electrochemical cycling of diluted LOHC was primarily contributed to by the LOHC distillation separation process. A sensitivity analysis showed the carbon footprint LOHC concentration dependence during the electrochemical cycling process. Moreover, the electrolyte composition significantly affects the carbon footprint during electrochemical LOHC cycling. Energy utilization, water usage, and toxicity for electrochemical LOHC cycling are discussed to provide an overview for better economic and environmental practices. There are significant opportunities in the electrochemical cycling of LOHCs if appropriate conditions such as high concentrations of reactant, reversible redox cycling ability, high Faradaic efficiencies, and catalyst stabilities are achieved.

25 ENERGY STORAGE↗
DOE OSTI2024

Identifying Green Solvent Mixtures for Bioproduct Separation Using Bayesian Experimental Design

Liquid–liquid extraction (LLE) is a widely used technique for the separation and purification of liquid-phase products with applications in various industries, including pharmaceuticals, petrochemicals, and renewable chemistry. A critical step in the design of an LLE process is the selection of appropriate solvents. This study presents a new methodology for identifying solvent mixtures for bioproduct separation using Bayesian experimental design (BED). Motivated by the need for environmentally friendly and effective separation methods, we address the challenge of selecting solvent systems that balance separation efficiency, selectivity, and environmental impact while also tackling the difficulty of separating multiple bioproducts using complex solvent systems. Our approach specifically seeks to predict product partition coefficients (log10 Kp values) as thermodynamic parameters underlying solvent selection. The iterative approach integrates Bayesian optimization with experimental measurements to guide solvent selection and leverages COSMO-RS simulations to enhance high-throughput experimentation. Using the design of solvent systems for the separation of lignin-derived aromatic products via centrifugal partition chromatography (CPC) as a case study, we show that within seven iterations/cycles of the methodology, we can identify new mixtures of green solvents that align with CPC design principles. Furthermore, these results demonstrate the efficacy of the BED framework in optimizing green solvent systems for complex separations, highlighting the potential of this method to advance the field of green chemistry and contribute to the development of sustainable industrial processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Techno-Economic Basis for Coproduct Manufacturing To Enable Hydrocarbon Fuel Production from Lignocellulosic Biomass

Biorefinery process development relies on techno-economic analysis (TEA) to identify primary cost drivers, prioritize research directions, and mitigate technical risk for scale-up through development of detailed process designs. Here, we conduct TEA of a model 2000 dry metric ton-per-day lignocellulosic biorefinery that employs a two-step pretreatment and enzymatic hydrolysis to produce biomass-derived sugars, followed by biological lipid production, lipid recovery, and catalytic hydrotreating to produce renewable diesel blendstock (RDB). On the basis of projected near-term technical feasibility of these steps, we predict that RDB could be produced at a minimum fuel selling price (MFSP) of USD $9.55/gasoline-gallon-equivalent (GGE), predicated on the need for improvements in the lipid productivity and yield beyond current benchmark performance. This cost is significant given the limitations in scale and high costs for aerobic cultivation of oleaginous microbes and subsequent lipid extraction/recovery. In light of this predicted cost, we developed an alternative pathway which demonstrates that RDB costs could be substantially reduced in the near term if upgradeable fractions of biomass, in this case hemicellulose-derived sugars, are diverted to coproducts of sufficient value and market size; here, we use succinic acid as an example coproduct. The coproduction model predicts an MFSP of USD $5.28/GGE when leaving conversion and yield parameters unchanged for the fuel production pathway, leading to a change in biorefinery RDB capacity from 24 to 15 MM GGE/year and 0.13 MM tons of succinic acid per year. Additional analysis demonstrates that beyond the near-term projections assumed in the models here, further reductions in the MFSP toward $2-3/GGE (which would be competitive with fossil-based hydrocarbon fuels) are possible with additional transformational improvements in the fuel and coproduct trains, especially in terms of carbon efficiency to both fuels and coproducts, recovery and purification of fuels and coproducts, and coproduct selection and price. Overall, this analysis documents potential economics for both a hydrocarbon fuel and bioproduct process pathway and highlights prioritized research directions beyond the current benchmark to enable hydrocarbon fuel production via an oleaginous microbial platform with simultaneous coproduct manufacturing from lignocellulosic biomass.

09 BIOMASS FUELS↗
DOE OSTI2017

Defective Carbon-Based Materials for the Electrochemical Synthesis of Hydrogen Peroxide

Hydrogen peroxide (H 2 O 2 ), an important industrial chemical, is currently produced through an energy-intensive anthraquinone process that is limited to large-scale facilities. Small-scale decentralized electrochemical production of H 2 O 2 via a two-electron oxygen reduction reaction (ORR) offers unique opportunities for sanitization applications and the purification of drinking water. The development of inexpensive, efficient, and selective catalysts for this reaction remains a challenge. Here in this paper, we examine two different porous carbon-based electrocatalysts and show that they exhibit high selectivity for H 2 O 2 under alkaline conditions. By rationally varying synthetic methods, we explore the effect of pore size on electrocatalytic performance. Furthermore, by means of density functional calculations, we point out the critical role of carbon defects. Our theory results show that the majority of defects in graphene are naturally selective for the two-electron reduction of O 2 to H 2 O 2 , and we identify the types of defects with high activity.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Environmental, Economic, and Scalability Considerations and Trends of Selected Fuel Economy-Enhancing Biomass-Derived Blendstocks

24 biomass-derived compounds and mixtures, identified based on their physical properties, that could be blended into fuels to improve spark ignition engine fuel economy were assessed for their economic, technology readiness, and environmental viability. These bio-blendstocks were modeled to be produced biochemically, thermochemically, or through hybrid processes. To carry out the assessment, 17 metrics were developed for which each bio-blendstock was determined to be favorable, neutral, or unfavorable. Cellulosic ethanol was included as a reference case. Overall, bio-blendstock yields in biochemical processes were lower than in thermochemical processes, in which all biomass, including lignin, is converted to a product. Bio-blendstock yields were a key determinant in overall viability. Key knowledge gaps included the degree of purity needed for use as a bio-blendstock as compared to a chemical. Less stringent purification requirements for fuels could cut processing costs and environmental impacts. Additionally, more information is needed on the blendability of many of these bio-blendstocks with gasoline to support the technology readiness evaluation. Overall, the technology to produce many of these blendstocks from biomass is emerging and as it matures, these assessments must be revisited. Importantly, considering economic, environmental, and technology readiness factors in addition to physical properties of blendstocks that could be used to boost fuel economy can help spotlight those most likely to be viable in the near term.

biofuels↗
DOE OSTI2018

Kinetics and Rheological Behavior of Higher Solid (Solids >20%) Enzymatic Hydrolysis Reactions Using Dilute Acid Pretreated, Deacetylation and Disk Refined, and Deacetylation and Mechanical Refined (DMR) Corn Stover Slurries

Many potential biochemical pathways producing advanced hydrocarbon fuels from renewable lignocellulosic biomass require hydrolysates with high sugar concentrations and low toxicity, enabling flexible fermentation strategies, such as fed-batch fermentations capable of producing high product titers and production rates during fermentation. High sugar concentrations also increase the osmotic pressure in the hydrolysates, thus helping to decrease contamination issues. We have shown the production of high sugar concentrations directly from biomass without the need for energy/capital intensive concentration, conditioning, and/or purification steps. In our previous work, we successfully demonstrated high biomass-derived sugar concentrations (over 230 g/L fermentable sugars) in enzymatic hydrolysis from high solid (>20 wt % insoluble solids) digestions of dilute alkali deacetylated and mechanically refined (DMR) corn stover slurries. The goal of this work was to understand the effects of initial solid loadings on differently pretreated corn stover substrates on the rheological property changes of enzymatic-hydrolyzed slurries as well as the rates and yields of the enzymatic hydrolysis reactions. We performed high-solid enzymatic hydrolysis using deacetylated and disk refined (DDR), DMR, and dilute acid pretreated (DAP) corn stover substrates at four different initial total solid loadings, 17, 22, 27, and 32%. Slurry samples were collected at regular intervals for measurements of monomeric and oligomeric sugar concentrations (glucose and xylose), particle size distributions, viscosities, and yield stresses. We produced over 270 g/L of fermentable, monomeric sugars (157 g/L of glucose and 114 g/L of xylose) at 32 wt % total insoluble solid during enzymatic hydrolysis of the DMR substrates. The pumpabilities of the digested, high-solid enzymatic hydrolysates were shown to be comparable to other commercially relevant slurry streams, such as honey, peanut butter, and ketchup from the food industry. The conversion and rheological results indicate that high-solid enzymatic hydrolysis (~33 wt %) of DMR substrates is a promising and scalable technology for producing high sugar concentration slurries from lignocellulosic biomass.

09 BIOMASS FUELS↗
DOE OSTI2019

Efficient Ammonia Decomposition in a Catalytic Membrane Reactor To Enable Hydrogen Storage and Utilization

Liquid ammonia is a high density (17.7 wt. %) hydrogen carrier with a well-established production and distribution infrastructure. Efficient decomposition and purification are essential for its use as a hydrogen storage material. Here we demonstrate the production of high purity (> 99.7%) H 2 from NH 3 using a catalytic membrane reactor (CMR) in which a Ru catalyst is impregnated within a porous yttria-stabilized zirconia (YSZ) tube coated with a thin, 6 µm Pd film by electroless deposition. The intimate proximity of catalyst and membrane eliminates transport resistances that limit performance in the conventional packed bed membrane reactor (PBMR) configuration. The addition of a Cs promoter enabled complete NH 3 conversion at temperatures as low as 400°C, exceeding equilibrium constraints without the need for a sweep gas. A reactor model was developed that captured CMR performance with high fidelity. NH 3 decomposition was observed to follow first order kinetics due to efficient H 2 removal. Relative to a comparable PBMR, the Ru loading in the CMR was reduced an order of magnitude and the H 2 recovery increased 35%, enabling record volumetric productivity rates (> 30 mol m-3 s-1) that validate its promise for efficient, compact H 2 delivery from ammonia.

08 HYDROGEN↗
DOE OSTI2019

Method to Regioselectively Iodine-Tag Free-Phenolic Aromatic End-Groups in Lignin for 1 H– 13 C-HSQC NMR Analysis

Phenolic end-groups on lignin molecules are vital sites for continued lignification, their influence over lignin molecular properties, their ability to enhance lignin degradation, and their potential for derivatization to produce lignin materials. Here we use iodination to regioselectively tag, and HSQC-NMR to monitor, guaiacyl phenolic aromatic end-groups in lignins. Using dimeric lignin models, iodination at the 5-position of the phenolic ring was shown to be clean, and almost quantitative. Additionally, the 6-position C/H correlation peak shifted downfield in both carbon and proton dimensions in HSQC spectra. As phenolic aromatic rings could be selectively iodinated, and as their C6/H6 aromatic signals appear in a clear region of HSQC NMR spectra (different from the original position), we would have a new method for tagging and analyzing such phenolic aromatic rings in lignins if the method could be applied to the polymer. The new tagging approach was therefore applied to a synthetic guaiacyl lignin polymer (DHP) and a milled wood lignin (MWL) isolated from Japanese cedar ( Cryptomeria japonica ). The derivatization proceeded directly in the NMR tube, without needing isolation or purification, from which HSQC-NMR revealed that the diagnostic C6/H6 correlations matched one from the dimeric model compound. This phenolic unit tagging method adds a useful method to the lignin structural analysis toolbox, helping to gain a better understanding of lignin’s phenolic end-units.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Robust Synthetic Biology Toolkit to Advance Carboxysome Study and Redesign

Carboxysomes are polyhedral protein organelles that microorganisms use to facilitate carbon dioxide assimilation. They are composed of a modular protein shell that envelops an enzymatic core mainly composed of physically coupled Rubisco and carbonic anhydrase. While the modular construction principles of carboxysomes make them attractive targets as customizable metabolic platforms, their size and complexity can be a hindrance. In this work, we design and validate a plasmid set, the pXpressome toolkit, in which α-carboxysomes are robustly expressed and remain intact and functional after purification. We tested this toolkit by introducing mutations that influence carboxysome structure and performance. We find that deletion of vertex-capping genes results in formation of larger carboxysomes, while deletion of facet forming genes produces smaller particles, suggesting that adjusting the ratio of these proteins can rationally affect morphology. Through a series of fluorescently labeled constructs, we observe that this toolkit leads to more uniform expression and better cell health than previously published carboxysome expression systems. Overall, the pXpressome toolkit facilitates the study and redesign of carboxysomes with robust performance and improved phenotype uniformity. The pXpressome toolkit will support efforts to remodel carboxysomes for enhanced carbon fixation or serve as a platform for other nanoencapsulation goals.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Operando Synthesis of Macroporous Molybdenum Diselenide Films for Electrocatalysis of the Hydrogen-Evolution Reaction

The catalytically inactive components of a film have been converted, through an operando method of synthesis, to produce a catalyst for the reaction that the film is catalyzing. Specifically, thin films of molybdenum diselenide have been synthesized using a two-step wet-chemical method, in which excess sodium selenide was first added to a solution of ammonium heptamolydbate in aqueous sulfuric acid, resulting in the spontaneous formation of a black precipitate that contained molybdenum triselenide (MoSe 3 ), molybdenum trioxide (MoO 3 ), and elemental selenium. After purification and after the film had been drop cast onto a glassy carbon electrode, a reductive potential was applied to the precipitate-coated electrode. Hydrogen evolution occurred within the range of potentials applied to the electrode, but during the initial voltammetric cycle, an overpotential of ~400 mV was required to drive the hydrogen-evolution reaction at a benchmark current density of –10 mA cm –2 . The overpotential required to evolve hydrogen at the benchmark rate progressively decreased with subsequent voltammetry cycles, until a steady state was reached at which only ~250 mV of overpotential was required to pass –10 mA cm –2 of current density. During the electrocatalysis, the catalytically inactive components in the as-prepared film were (reductively) converted to MoSe 2 through an operando method of synthesis of the hydrogen-evolution catalyst. The initial film prepared from the precipitate was smooth, but the converted film was completely covered with pores ~200 nm in diameter. In conclusion, the porous MoSe 2 film was stable while being assessed by cyclic voltammetry for 48 h, and the overpotential required to sustain 10 mA cm –2 of hydrogen evolution increased by <50 mV over this period of operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Ultraclean Fuels Production and Utilization for the Twenty-First Century: Advances toward Sustainable Transportation Fuels

Ultraclean fuels production has become increasingly important as a method to help decrease emissions and allow the introduction of alternative feed stocks for transportation fuels. Established methods, such as Fischer-Tropsch, have seen a resurgence of interest as natural gas prices drop and existing petroleum resources require more intensive clean-up and purification to meet stringent environmental standards. This review covers some of the advances in deep desulfurization, synthesis gas conversion into fuels and feed stocks that were presented at the 245th American Chemical Society Spring Annual Meeting in New Orleans, LA in the Division of Energy and Fuels symposium on "Ultraclean Fuels Production and Utilization".

02 PETROLEUM↗
DOE OSTI2012

Degradation of CYANEX 301 in Contact with Nitric Acid Media

The nature of the degradation product obtained upon contacting CYANEX 301 (bis(2,4,4-trimethylpentyl)dithiophosphinic acid) with nitric acid has been elucidated and found to be a disulfide derivative. The first step to the degradation of CYANEX 301 in toluene has been studied using 31P{1H} NMR after being contacted with nitric acid media. The spectrum of the degradation product exhibits a complex multiplet around dP = 80 ppm. A succession of purifications of CYANEX 301 has resulted in single crystals of the acidic form and the corresponding ammonium salt. Unlike the original CYANEX 301, which consists of a complex diastereomeric mixture displaying all possible combinations of chiral orientations at the 2-methyl positions, the purified crystals were shown by single-crystal X-ray diffraction to be racemates, containing 50:50 mixtures of the [R;R] and [S;S] diastereomers. The comparison between the 31P {1H} NMR spectra of the degradation products resulting from the diastereomerically pure CYANEX 301 and the original diastereomeric mixture has elucidated the influence of the isomeric composition on the multiplicity of the 31P {1H} NMR peak. These NMR data indicate the initial degradation leads to a disulfide-bridged condensation product displaying multiple resonances due to phosphorus–phosphorus coupling, which is caused by the inequivalence of the two P atoms as a result of their different chirality. A total of nine different NMR resonances, six of which display phosphorus–phosphorus coupling, could be assigned, and the identity of the peaks corresponding to phosphorus atoms coupled to each other was confirmed by 31P {1H} homodecoupled NMR analysis.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2012

Dynamics of Uranyl Peroxide Nanocapsules

Discrete aqueous metal oxide polyionic clusters that include aluminum polycations, transition-metal polyoxometalates, and the actinyl peroxide clusters have captivated the interest of scientists in the realm of both their fundamental and applied chemistries. Yet the counterions for these polycations or polyanions are often ignored, even though they are imperative for solubility, crystallization, purification, and even templating cluster formation. The actinyl peroxide clusters have counterions not only external, but internal to the hollow peroxide capsules. In this study, we reveal the dynamic behavior of these internal alkali counterions via solid-state and liquid NMR experiments. These studies on two select cluster geometries, those containing 24 and 28 uranyl polyhedra, respectively, show that the capsules-like clusters are not rigid entities. Rather, the internal alkalis both have mobility inside the capsules, as well as exchange with species in the media in which they are dissolved. The alkali mobilities are affected by both what is inside the clusters as well as the composition of the dissolving medium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗