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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

A generalized computational framework to streamline thermodynamics and kinetics analysis of metabolic pathways

Metabolic engineering is a critical biotechnological approach in addressing global energy and environment challenges. Most engineering efforts, however, consist of laborious and inefficient trial-and-error of target pathways, due in part to the lack of methodologies that can comprehensively assess pathway properties in thermodynamics and kinetics. Metabolic engineering can benefit from computational tools that evaluate feasibility, expense and stability of non-natural metabolic pathways. Such tools can also help us understand natural pathways and their regulation at systems level. Here we introduce a computational toolbox, PathParser, which, for the first time, integrates multiple important functions for pathway analysis including thermodynamics analysis, kinetics-based protein cost optimization and robustness analysis. Specifically, PathParser enables optimization of the driving force of a pathway by minimizing the Gibbs free energy of least thermodynamically favorable reaction. In addition, based on reaction thermodynamics and enzyme kinetics, it can compute the minimal enzyme protein cost that supports metabolic flux, and evaluate pathway stability and flux in response to enzyme concentration perturbations. In a demo analysis of the Calvin-Benson-Bassham cycle and photorespiration pathway in the model cyanobacterium Synechocystis PCC 6803, the computation results are corroborated by experimental proteomics data as well as metabolic engineering outcomes. This toolbox may have broad application in metabolic engineering and systems biology in other microbial systems.

09 BIOMASS FUELS↗
DOE OSTI2020

A Multidimensional Operando Study Showing the Importance of the Electrode Macrostructure in Lithium Sulfur Batteries

Lithium sulfur batteries are one of the most promising next-generation energy storage technologies, because of their impressive theoretical energy density, low materials cost, and relative safety. However, incomplete understanding of their underlying operation mechanisms has hindered their further development and commercialization. In this work, to gain a better understanding of the operation mechanisms in the lithium sulfur battery, three macroscopically different (woven and nonwoven) and microscopically similar (made from the same carbon fibers) free-standing carbon felts are used as the conductive matrices to show how the macrostructure influences the redox reactions and the electrochemical performance. Additionally, an operando radiography and simultaneous in situ electrochemical impedance spectroscopy study are performed to highlight the differences of the carbon hosts and how they compare electrochemically in a lithium sulfur battery. The electrochemical results show that the carbon host with a more open structure results in increased capacity as well as a higher diffusion coefficient. The operando radiography shows that the open structures are more conducive to efficient redox reactivity in forming solid sulfur species, mostly in the form of elongated needlelike structures identified as β-S8, near the end of charge, which is corroborated by the impedance data. The data also reveal a “breathing” mechanism, where the polysulfides are pushed to the edges during discharge and pulled back during charge. Furthermore, it is also revealed that the “breathing” process is a limiting factor in the high rate performance. Overall, this study shows that there is a close relationship between the macrostructure of the carbon matrix and the electrochemical performance of the sulfur cathode.

25 ENERGY STORAGE↗
DOE OSTI2015

New information on the occurrence of the O(6) symmetry in nuclei

New γγ-coincidence relations and E2 decay transition rates in the isotopes 194,196 Pt have been deduced from γ-ray spectroscopy experiments using the Gammasphere spectrometer in projectile-Coulomb excitation reactions of beams of 194,196 Pt ions provided by the ATLAS accelerator facility. The results give access to observables that are crucial for a classification of excited quadrupole-collective states in terms of quantum numbers associated with the analytically solvable O(6) dynamical symmetry of the interacting boson model. The data on 196 Pt corroborate the qualitative pattern of excitation energies and E2 transition rates expected from the O(6) solution but the excitation energies significantly deviate from it on a quantitative level.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2014

Exotic exchange bias at epitaxial ferroelectric-ferromagnetic interfaces

Multiferroics in spintronics have opened up opportunities for future technological developments, particularly in the field of ferroelectric (FE)-ferromagnetic (FM) oxide interfaces with functionalities. We find strong exchange bias shifts (up to 84 Oe) upon field cooling in metal-oxide (Fe/BaTiO{sub 3}) films combining FM and FE layers. The saturation magnetic moment of the FM layer is also significantly higher than in bulk (3.0 ± 0.2 μ{sub B}/atom) and the reversal mechanism occurs via a domain nucleation process. X-ray absorption spectroscopy at the Fe K-edge and Ba L3-edge indicate presence of few monolayers of antiferromagnetic FeO at the interface without the formation of any BaFeO{sub 3} layer. Polarized neutron reflectometry corroborates with our magnetization data as we perform depth profiling of the magnetic and structural densities in these bilayers. Our first principles density functional calculations support the formation of antiferromagnetic FeO layers at the interface along with an enhancement of Fe magnetic moments in the inner ferromagnetic layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

A Hybrid Approach Enabling Large-Scale Glycomic Analysis of Post-Golgi Vesicles Reveals a Transport Route for Polysaccharides

The plant endomembrane system facilitates the transport of polysaccharides, associated enzymes, and glycoproteins through its dynamic pathways. Although enzymes involved in cell wall biosynthesis have been identified, little is known about the endomembrane-based transport of glycan components. This is partially attributed to technical challenges in biochemically determining polysaccharide cargo in specific vesicles. Here, we introduce a hybrid approach addressing this limitation. By combining vesicle isolation with a large-scale carbohydrate antibody arraying technique, we charted an initial large-scale map describing the glycome profile of the SYNTAXIN OF PLANTS61 (SYP61) trans-Golgi network compartment in Arabidopsis (Arabidopsis thaliana). A library of antibodies recognizing specific noncellulosic carbohydrate epitopes allowed us to identify a range of diverse glycans, including pectins, xyloglucans (XyGs), and arabinogalactan proteins in isolated vesicles. Changes in XyG- and pectin-specific epitopes in the cell wall of an Arabidopsis SYP61 mutant corroborate our findings. Our data provide evidence that SYP61 vesicles are involved in the transport and deposition of structural polysaccharides and glycoproteins. Finally, adaptation of our methodology can enable studies characterizing the glycome profiles of various vesicle populations in plant and animal systems and their respective roles in glycan transport defined by subcellular markers, developmental stages, or environmental stimuli.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Nitrogen increases early‐stage and slows late‐stage decomposition across diverse grasslands

1. To evaluate how increased anthropogenic nutrient inputs alter carbon cycling in grasslands, we conducted a litter decomposition study across 20 temperate grasslands on three continents within the Nutrient Network, a globally distributed nutrient enrichment experiment 2. We determined the effects of addition of experimental nitrogen (N), phosphorus (P) and potassium plus micronutrient (K μ ) on decomposition of a common tree leaf litter in a long-term study (maximum of 7 years; exact deployment period varied across sites). The use of higher order decomposition models allowed us to distinguish between the effects of nutrients on early- versus late-stage decomposition. 3. Across continents, the addition of N (but not other nutrients) accelerated early-stage decomposition and slowed late-stage decomposition, increasing the slowly decomposing fraction by 28% and the overall litter mean residence time by 58%. 4. Synthesis. Using a novel, long-term cross-site experiment, we found widespread evidence that N enhances the early stages of above-ground plant litter decomposition across diverse and widespread temperate grassland sites but slows late-stage decomposition. These findings were corroborated by fitting the data to multiple decomposition models and have implications for N effects on soil organic matter formation. For example, following N enrichment, increased microbial processing of litter substrates early in decomposition could promote the production and transfer of low molecular weight compounds to soils and potentially enhance the stabilization of mineral-associated organic matter. By contrast, by slowing late-stage decomposition, N enrichment could promote particulate organic matter (POM) accumulation. Such hypotheses deserve further testing.

Nutrient Network (NutNet)↗
DOE OSTI2020

Multiplicity dependence of (multi-)strange hadron production in proton-proton collisions at $\sqrt{s}$s = 13 TeV

The production rates and the transverse momentum distribution of strange hadrons at mid-rapidity ( | y | < 0.5 ) are measured in proton-proton collisions at $\sqrt{s}$ = 13 TeV as a function of the charged particle multiplicity, using the ALICE detector at the LHC. The production rates of K$^0_S$, Λ, &#x039E;<!-- Ξ --> , and Ω ncrease with the multiplicity faster than what is reported for inclusive charged particles. The increase is found to be more pronounced for hadrons with a larger strangeness content. Possible auto-correlations between the charged particles and the strange hadrons are evaluated by measuring the event-activity with charged particle multiplicity estimators covering different pseudorapidity regions. When comparing to lower energy results, the yields of strange hadrons are found to depend only on the mid-rapidity charged particle multiplicity. Several features of the data are reproduced qualitatively by general purpose QCD Monte Carlo models that take into account the effect of densely-packed QCD strings in high multiplicity collisions. However, none of the tested models reproduce the data quantitatively. This work corroborates and extends the ALICE findings on strangeness production in proton-proton collisions at 7 TeV.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
NASA NTRS1976

Stratospheric measurement requirements and satellite-borne remote sensing capabilities

The capabilities of specific NASA remote sensing systems to provide appropriate measurements of stratospheric parameters for potential user needs were assessed. This was used to evaluate the capabilities of the remote sensing systems to perform global monitoring of the stratosphere. The following conclusions were reached: (1) The performance of current remote stratospheric sensors, in some cases, compares quite well with identified measurement requirements. Their ability to measure other species has not been demonstrated. (2) None of the current, in-situ methods have the capability to satisfy the requirements for global monitoring and the temporal constraints derived from the users needs portion of the study. (3) Existing, non-remote techniques will continue to play an important role in stratospheric investigations for both corroboration of remotely collected data and in the evolutionary development of future remote sensors.

Carmichael, J. J.↗
NASA NTRS1976

Monitoring of environmental effects of coal strip mining from satellite imagery

This paper evaluates satellite imagery as a means of monitoring coal strip mines and their environmental effects. The satellite imagery employed is Skylab EREP S-190A and S-190B from SL-2, SL-3 and SL-4 missions; a large variety of camera/film/filter combinations has been reviewed. The investigation includes determining the applicability of satellite imagery for detection of disturbed acreage in areas of coal surface mining as well as the much more detailed monitoring of specific surface-mining operations, including: active mines, inactive mines, highwalls, ramp roads, pits, water impoundments and their associated acidity, graded areas and types of grading, and reclamed areas. Techniques have been developed to enable mining personnel to utilize this imagery in a practical and economic manner, requiring no previous photo-interpretation background and no purchases of expensive viewing or data-analysis equipment. To corroborate the photo-interpretation results, on-site observations were made in the very active mining area near Madisonville, Kentucky.

Brooks, R. L.↗
NASA NTRS1986

Temperatures of quiescent prominences measured from hydrogen Paschen and CaII IR lines

During 12 to 17 September 1983 a number of prominences were observed with the McMatch solar telescope of National Solar Observatories, using the Fourier transform spectrometer with a InSb detector (Brault 1979). The present study refers to three prominences observed 13 and 14 September. Prominence A: Large quiescent prominence at S28 E90 Prominence B. Stable prominence in weakly enhanced magnetic region at about NO8 E90 Prominence C: Quiescent prominence at N30 E90. Spectra were obtained at a total of 15 different locations in the three prominences in the wavelength range lambda, lambda 7740 to 14,000 Angstroms. The observed differences between T sub exc and T sub kin are hardly significant. Researchers conclude that the two methods for temperature determination when applied to optically thin lines give reasonably consistent results, i.e., the population of the excited levels of hydrogen is collisionally controlled. The well known increase in T and V towards the edge of equiescent prominences (Hirayama 1964) is not corroborated by the present data. One explanation for this could be that prominence A is atypical. The optical thickness of prominence emission lines tends to increase from center to edges as demonstrated by the case of He I lambda 10830 angstroms. If line opacity plays a significant role in earlier center to edge determinations of T and V, a smaller variation would be expected from measurements in optically thin lines, such as in the present case.

Engvold, Oddbjorn↗
NASA NTRSDate not supplied

X-Ray Diffraction Based Phase Identification in NiTiHf Shape Memory Alloys with Variable Hf Content

NiTiHf type shape memory alloys have been studied for use in high temperature actuator applications, the most studied of which is the NiTi-20Hf atomic % composition. In this study, six samples of NiTi-Hf including 20Hf, 30Hf, 35Hf, 40Hf, 45Hf, and 50Hf were evaluated by both 1D and 2D X-ray diffraction (XRD) to elucidate what phases and crystal structures were present at room temperature. Given small sample sizes and relatively large grains, multiple cross-sections were measured to increase the sampling statistics, and 2D XRD frames were collected to corroborate the 1D XRD data. Rietveld and structureless refinements were both performed, allowing for adjustments in orientation lattice constant, and structure factor. At room temperature, the primary martensitic phase in the NiTiHf alloys with 20 at% and lower Hf is a monoclinic B19’ phase (P1121/m space group). This phase was identifiable, even in small amounts, in the higher Hf samples. The primary phase in the 30 -50 at% Hf samples is an orthorhombic B33 (Cmcm space group) phase. This work supported thermal analyses indicating the phase transition paths from the two different room temperature martensitic phases to the B2 austenitic phase.

Laura Wilson↗
DOE OSTI2018

Solar Buyer's Markets: Unlocking Lower Photovoltaic and Battery Prices on Online Quote Platforms

Previous NREL research shows that solar photovoltaic (PV) customers tend to obtain lower installation quote prices on online quote platforms. In new research reported in Solar Buyer's Markets: Unlocking Lower Photovoltaic and Battery Prices on Online Quote Platforms, we corroborate those results using data from the Pick My Solar quote platform. Furthermore, for the first time, we evaluate quote prices for batteries on online quote platforms. Given that few customers currently use quote platforms, we discuss various pathways to increase use of online quote platforms, including developing strategic partnerships, building customer trust, increasing market transparency, and providing quality guarantees.

14 SOLAR ENERGY↗
DOE OSTI2012

Assessment of Geothermal Resource Potential at a High-Priority Area on the Utah Testing and Training Range–South (UTTR–S)

Field investigations conducted during 2011 support and expand the conclusion of the original Preliminary Report that discovery of a viable geothermal system is possible in the northwestern part of the Utah Testing and Training Range-South (UTTR-S), referred to henceforth as Focus Area 1. The investigations defined the southward extent of the Wendover graben into and near Focus Area 1, enhanced the understanding of subsurface conditions, and focused further geothermal exploration efforts towards the northwestern-most part of Focus Area 1. Specifically, the detailed gravity survey shows that the Wendover graben, first defined by Cook et al. (1964) for areas north of Interstate Highway 80, extends and deepens southwest-ward to the northwest corner of Focus Area 1. At its deepest point, the intersection with a northwest-trending graben there is favorable for enhanced permeability associated with intersecting faults. Processing and modeling of the gravity data collected during 2011 provide a good understanding of graben depth and distribution of faults bounding the graben and has focused the interest area of the study. Down-hole logging of temperatures in wells made available near the Intrepid, Inc., evaporation ponds, just north of Focus Area 1, provide a good understanding of the variability of thermal gradients in that area and corroborate the more extensive temperature data reported by Turk (1973) for the depth range of 300-500 m. Moderate temperature gradients in the northern part of the Intrepid area increase to much higher gradients and bottom-hole temperatures southeastward, towards graben-bounding faults, suggesting upwelling geothermal waters along those faults. Water sampling, analysis, and temperature measurements of Blue Lakes and Mosquito Willey's springs, on the western boundary of Focus Area 1, also show elevated temperatures along the graben-bounding fault system. In addition, water chemistry suggests origin of those waters in limestone rocks beneath the graben in areas with temperatures as high as 140 C (284 F). In conclusion, all of the field data collected during 2011 and documented in the Appendices of this report indicate that there is reasonable potential for a viable geothermal resource along faults that bound the Wendover graben. Prospects for a system capable of binary electrical generation are especially good, and the possibility of a flash steam system is also within reason. The next steps should focus on securing the necessary funding for detailed geophysical surveys and for drilling a set of temperature gradient wells to further evaluate the resource, and to focus deep exploration efforts in the most promising areas.

15 GEOTHERMAL ENERGY↗
DOE OSTI2020

Model 9975 O-Ring Fixture Long-Term Leak Performance (FY2020 Status Report)

Leak testing experiments to monitor the aging performance of Viton GLT and GLT-S O-rings used in the model 9975 shipping package has been ongoing since 2004 at Savannah River National Laboratory. Seventy tests using mock-up 9975 primary containment vessels (PCVs) with GLT O-rings were assembled and heated to temperatures ranging from 200 to 450 °F. In addition, fourteen tests with GLT-S O-rings were initiated in 2008 and heated to temperatures ranging from 200 to 400 °F. The conditioning temperatures are elevated compared to the calculated maximum O-ring temperature in a 9975 package in storage, 158 °F, to accelerate aging and enable observations of O-ring failures in a reasonable time frame. The fixtures are leak tested periodically and all GLT O-ring fixtures aging at 350 °F or above have failed to maintain a leak-tight seal. Eight GLT O-ring fixtures aging at 300 °F have failed after 2.8 to 5.7 years at temperature while the remaining fixtures at 300 °F were retired from testing following more than five years without failure. No failures have yet been observed in GLT O-ring fixtures aging at 200 °F for 12 to 14 years or aging at 270 °F for 8.5 years. All GLT-S O-ring fixtures aging at 300 °F or above have failed their leak test. No failures have yet been observed in GLT-S O-ring fixtures aging at 200 and 250 °F for 10 to 10.5 years. Data from the O-ring fixtures are generally consistent with results from compression stress-relaxation testing, and provide confidence in the predictive models based on those results. However, uncertainty exists in extrapolating these elevated temperature results to the lower temperatures of interest for normal storage in K-Area Complex (KAC). Oxygen consumption testing, which includes results from temperatures near KAC normal storage temperatures, is ongoing to provide further confidence and corroborate these extrapolations. The collective data from these test efforts suggest the minimum O-ring service life at KAC normal storage conditions should be at least 34 years for GLT and GLT-S O-rings. Measurement of compression set in O-rings removed from failed fixtures, compared to that from KAC surveillance O-rings, indicates margin remains for O-rings still in service. Aging and periodic leak testing will continue for the remaining PCV fixtures.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Model 9975 O Ring Fixture LongTerm Leak Performance (FY2021 Status Report)

Leak testing experiments to monitor the aging performance of Viton® GLT and GLT-S O-rings used in the model 9975 shipping package has been ongoing since 2004 at Savannah River National Laboratory. Seventy tests using mock-up 9975 primary containment vessels (PCVs) with GLT O-rings were assembled and heated to temperatures ranging from 200 to 450 °F. Due to material substitution, fourteen tests with GLT-S O-rings were initiated in 2008 and heated to temperatures ranging from 200 to 400 °F. The conditioning temperatures are elevated compared to the calculated maximum O-ring temperature in a 9975 package in storage, 158 °F, to accelerate aging and enable observations of O-ring failures in a reasonable time frame. The fixtures are leak tested periodically and all GLT O-ring fixtures aging at 350 °F or above have failed to maintain a leak-tight seal. Eight GLT O-ring fixtures aging at 300 °F have failed after 2.8 to 5.7 years at temperature while the remaining fixtures at 300 °F were retired from testing following more than five years without failure. There has been one GLT O-ring fixture which failed after 13.4 years aging at 200 °F. However, 19 other GLT O-rings aging at 200 °F have remained leak-tight for over 14 years and remain in test. No failures have yet been observed in GLT O-ring fixtures aging at 270 °F for 9.5 years. All GLT-S O-ring fixtures aging at 300 °F or above have failed their leak test. No failures have yet been observed in GLT-S O-ring fixtures aging at 200 and 250 °F for 11.5 years. Data from the O-ring fixtures are generally consistent with results from compression stress-relaxation testing, and provide confidence in the predictive models based on those results. However, uncertainty exists in extrapolating these elevated temperature results to the lower temperatures of interest for normal storage in K-Area Complex (KAC). Oxygen consumption testing, which includes results from temperatures near KAC normal storage temperatures, is ongoing to provide further confidence and corroborate these extrapolations. The collective data from these test efforts suggest the minimum O-ring service life at KAC normal storage conditions should be at least 34 years for GLT and GLT-S O-rings. Measurement of compression set in O-rings removed from failed fixtures, compared to that from KAC surveillance O-rings, indicate significant margin remains for O-rings still in service in 9975 packages in KAC. Aging and periodic leak testing will continue for the remaining 26 mock-up PCV fixtures.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Model 9975 O-Ring Fixture Long-Term Leak Performance (FY2022 Status Report)

Leak testing experiments to monitor the aging performance of Viton® GLT and GLT-S O-rings used in the model 9975 shipping package has been ongoing since 2004 at Savannah River National Laboratory. Seventy tests using mock-up 9975 primary containment vessels (PCVs) with GLT O-rings were assembled and heated to temperatures ranging from 200 to 450 °F. Due to material substitution, fourteen tests with GLT-S O-rings were initiated in 2008 and heated to temperatures ranging from 200 to 400 °F. The conditioning temperatures are elevated compared to the calculated maximum O-ring temperature in a 9975 package in storage, 158 °F, to accelerate aging and enable observations of O-ring failures in a reasonable time frame. The fixtures are leak tested periodically and all GLT O-ring fixtures aging at 350 °F or above have failed to maintain a leak-tight seal. Eight GLT O-ring fixtures aging at 300 °F have failed after 2.8 to 5.7 years at temperature while the remaining fixtures at 300 °F were retired from testing following more than five years without failure. There has been one GLT O-ring fixture which failed after 13.4 years aging at 200 °F. However, 20 other GLT O-rings aging at 200 °F have remained leak-tight for over 14 years and remain in test. No failures have yet been observed in GLT O-ring fixtures aging at 270 °F for 10.4 years. All GLT-S O-ring fixtures aging at 300 °F or above have failed their leak test. No failures have yet been observed in GLT-S O-ring fixtures aging at 250 °F for 12.5 years. This year, one GLT-S O-ring fixture failed after 12.4 years aging at 200 °F. Data from the O-ring fixtures are generally consistent with results from compression stress-relaxation testing, and provide confidence in the predictive models based on those results. However, uncertainty exists in extrapolating these elevated temperature results to the lower temperatures of interest for normal storage in K-Area Complex (KAC). Oxygen consumption testing, which includes results from temperatures near KAC normal storage temperatures, is ongoing to provide further confidence and corroborate these extrapolations. The collective data from these test efforts suggest the minimum O-ring service life at KAC normal storage conditions should be at least 34 years for GLT and GLT-S O-rings. Measurement of compression set in O-rings removed from failed fixtures, compared to that from KAC surveillance O-rings, indicate significant margin remains for O-rings still in service in 9975 packages in KAC. Aging and periodic leak testing will continue for the remaining 25 mock-up PCV fixtures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Finding Liebig’s law of the minimum

Abstract Liebig’s law of the minimum (LLM) is often used to interpret empirical biological growth data and model multiple substrates co‐limited growth. However, its mechanistic foundation is rarely discussed, even though its validity has been questioned since its introduction in the 1820s. Here we first show that LLM is a crude approximation of the law of mass action, the state of art theory of biochemical reactions, and the LLM model is less accurate than two other approximations of the law of mass action: the synthesizing unit model and the additive model. We corroborate this conclusion using empirical data sets of algae and plants grown under two co‐limiting substrates. Based on our analysis, we show that when growth is modeled directly as a function of substrate uptake, the LLM model improperly restricts the organism to be of fixed elemental stoichiometry, making it incapable of consistently resolving biological adaptation, ecological evolution, and community assembly. When growth is modeled as a function of the cellular nutrient quota, the LLM model may obtain good results at the risk of incorrect model parameters as compared to those inferred from the more accurate synthesizing unit model. However, biogeochemical models that implement these three formulations are needed to evaluate which formulation is acceptably accurate and their impacts on predicted long‐term ecosystem dynamics. In particular, studies are needed that explore the extent to which parameter calibration can rescue model performance when the mechanistic representation of a biogeochemical process is known to be deficient.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

{sup 1}H and {sup 23}Na MAS NMR spectroscopy of cationic species in CO{sub 2} selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange

The location of extraframework cations in Sr{sup 2+} and Ba{sup 2+} ion-exchanged SAPO-34 was estimated by means of {sup 1}H and {sup 23}Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO{sub 2} adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium. - Graphical abstract: MAS NMR was used to elucidate the position the cationic species in alkaline earth metal exchanged silicoaluminophosphates. These species played a significant role during the ion exchange process and, therefore, the materials ultimate CO{sub 2} adsorption performance. Highlights: Black-Right-Pointing-Pointer Location of extraframework Sr{sup 2+} or Ba{sup 2+} cations was estimated by means of {sup 1}H and {sup 23}Na MAS NMR. Black-Right-Pointing-Pointer Level of Sr{sup 2+} or Ba{sup 2+} ion exchange was limited by the presence of protons and sodium cations. Black-Right-Pointing-Pointer Presence of ammonium cations in the supercages facilitated the exchange. Black-Right-Pointing-Pointer Sr{sup 2+} and Ba{sup 2+} ion exchanged SAPOs are outstanding CO{sub 2} adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗