Off-resonance 13C–2H REDOR NMR for site-resolved studies of molecular motion
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Biochemistry & Molecular Biology↗
SEARCH · Engineering Papers
Results for “NMR Spectroscopy”
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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In situ characterization of metastable Pb3O5 and Pb2O3 phases during thermal decomposition of PbO2 to PbO
Nonstoichiometric lead oxides play a key role in the formation and cycling of the positive electrodes in a lead acid battery. These phases have been linked to the underutilization of the positive active material but also play a key role in the battery’s cycle life, providing inter-particle adhesion and the connection to the underlying lead grid. Similar phases have previously been identified by mass loss or color change during thermal annealing of PbO2 to PbO, suggesting that at least two intermediate PbOx phases exist. Using multiple in situ analysis techniques (powder diffraction, x-ray absorption, x-ray photoelectron spectroscopy) and ex situ nuclear magnetic resonance measurements, the structural conversion and changes in the lead oxidation states were identified during this process. Isolation of the PbOx phases enabled confirmation of Pb3O5 and Pb2O3 by diffraction and the first 207Pb NMR measurement of these intermediates.
Kinnibrugh, Tiffany L.↗
Conversion of Phenolic Oil from Biomass Pyrolysis into Phenyl Esters
Bio-oil is among the most economical approaches for advanced biofuel production. However, bio-oil faces several challenges including high acidity and viscosity, poor storage, and thermal stability. This study focuses on the upgradation of lignocellulosic (corn stover and yellow pine) bio-oil derived phenolic oil (PO), produced by the autothermal fast pyrolysis, through acid-catalyzed esterification reaction. Our strategy exploits a little recognized chemistry: the Fischer esterification of PO and carboxylic acids into carboxylic acid phenyl esters (CAPE) using Dean Stark distillation. Analyses by the Folin–Ciocalteu method, Karl Fischer titration, gas chromatography flame ionization detector, and the molecular weight determination by gel permeation chromatography suggest the conversion of 50 wt% added phenolics to their corresponding CAPE. The Fourier transform infrared spectroscopy analysis confirmed the formation of new C=O and two C–O stretching bands and decrease in the intensity of phenolic-OH bands in the CAPE. The 13 C NMR analysis supports the formation of CAPE together with some unreacted precursors. A base-catalyzed ester hydrolysis experiment and mass balance calculation show an excellent agreement (within 5% range) of the equivalent weight between the produced ester and the phenyl hexanoate. Brookfield analysis indicates that CAPE has 330-fold lower viscosity than starting PO. Heating values of CAPE were higher than PO, from which they were derived (42.2 and 43.6%, respectively, for PO from pyrolysis of corn stover and yellow pine), while moisture content decreased by 98.3 and 98.7%, respectively. The CAPE, which is a phenolic analogue of methyl esters used in biodiesel, has improved stability compared to PO from which it was derived.
42 ENGINEERING↗
Eu(III) and Cm(III) Complexation by the Aminocarboxylates NTA, EDTA, and EGTA Studied with NMR, TRLFS, and ITC—An Improved Approach to More Robust Thermodynamics
The complex formation of Eu(III) and Cm(III) was studied via tetradentate, hexadentate, and octadentate coordinating ligands of the aminopolycarboxylate family, viz., nitrilotriacetate (NTA 3- ), ethylenediaminetetraacetate (EDTA 4- ), and ethylene glycol-bis(2-aminoethyl ether)-N,N,N',N'-tetraacetate (EGTA 4- ), respectively. Based on the complexones’ pK a values obtained from 1 H nuclear magnetic resonance (NMR) spectroscopic pH titration, complex formation constants were determined by means of the parallel-factor-analysis-assisted evaluation of Eu(III) and Cm(III) time-resolved laser-induced fluorescence spectroscopy (TRLFS). This was complemented by isothermal titration calorimetry (ITC), providing the enthalpy and entropy of the complex formation. This allowed us to obtain genuine species along with their molecular structures and corresponding reliable thermodynamic data. The three investigated complexones formed 1:1 complexes with both Eu(III) and Cm(III). Besides the established Eu(III)–NTA 1:1 and 1:2 complexes, we observed, for the first time, the existence of a Eu(III)–NTA 2:2 complex of millimolar metal and ligand concentrations. Demonstrated for thermodynamic studies on Eu(III) and Cm(III) interaction with complexones, the utilized approach is commonly applicable to many other metal–ligand systems, even to high-affinity ligands.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Thermodynamic evidence for a two-component superconducting order parameter in Sr 2 RuO 4
Sr 2 RuO 4 has stood as the leading candidate for a spin-triplet superconductor for 26 years. However, recent NMR experiments have cast doubt on this candidacy and it is difficult to find a theory of superconductivity that is consistent with all experiments. Here, the order parameter symmetry for this material therefore remains an open question. Symmetry-based experiments are needed that can rule out broad classes of possible superconducting order parameters. Here, we use resonant ultrasound spectroscopy to measure the entire symmetry-resolved elastic tensor of Sr 2 RuO 4 through the superconducting transition. We observe a thermodynamic discontinuity in the shear elastic modulus c 66 , which implies that the superconducting order parameter has two components. A two-component p-wave order parameter, such as p x + ip y , naturally satisfies this requirement. As this order parameter appears to have been precluded by recent NMR experiments, we suggest that two other two-component order parameters, namely {d xz ,d yz } and {d x 2 –y 2 ,g xy (x 2 –y 2 ) }, are now the prime candidates for the order parameter of Sr 2 RuO 4 .
36 MATERIALS SCIENCE↗
Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods
Mononuclear Fe ions ligated by nitrogen (FeN x ) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O 2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure–reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN x active centers. In the present study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeN x centers in Fe- N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO 2 – on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeN x sites or the coexistence of aggregated Fe species in addition to FeN x . The FeN x site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. Furthermore, the kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and analytical instrumentation (e.g., NMR).
36 MATERIALS SCIENCE↗
The origin, composition and history of cometary ices from spectroscopic studies
The spectroscopic analysis of pristine cometary material provides a very important probe of the chemical identity of the material as well as of the physical and chemical conditions which prevailed during the comet's history. Concerning classical spectroscopy, the spectral regions which will most likely prove most useful are the infrared, the visible and ultraviolet. Newer spectroscopic techniques which have the potential to provide equally important information include nuclear magnetic resonance (NMR) and electron spin resonance (ESR). Each technique is summarized with emphasis placed on the kind of information which can be obtained.
Allamandola, L. J.↗
Ab initio modeling and experimental investigation of Fe 2 P by DFT and spin spectroscopies
Fe 2 P alloys have been identified as promising candidates for magnetic refrigeration at room-temperature and for custom magnetostatic applications. The intent of this study is to accurately characterize the magnetic ground state of the parent compound, Fe 2 P, with two spectroscopic techniques, μSR and NMR, in order to provide solid bases for further experimental analysis of Fe 2 P-type transition metal based alloys. Herein, we perform zero applied field measurements using both techniques below the ferromagnetic transition T C = 220 K. The experimental results are reproduced and interpreted using first principles simulations, validating this approach for quantitative estimates in alloys of interest for technological applications.
36 MATERIALS SCIENCE↗
Investigation of glass-ceramic lithium thiophosphate solid electrolytes using NMR and neutron scattering
Solid-state Li batteries require solid electrolytes which have high Li+ conductivity and good chemical/mechanical compatibility with Li metal anodes and high energy cathodes. Structure/function correlations which relate local bonding to macroscopic properties are needed to guide development of new solid electrolyte materials. This study combines diffraction measurements with solid-state nuclear magnetic resonance spectroscopy (ssNMR) and neutron pair distribution function (nPDF) analysis to probe the short-range vs. long-range structure of glass-ceramic Li 3 PS 4 -based solid electrolytes. Here, we demonstrate how different synthesis conditions (e.g., solvent selection and thermal processing) affect the resulting polyanionic network. More specifically, structures with high P coordination numbers (e.g., PS 4 3– and P 2 S 7 4– ) correlate with higher Li + mobility compared to other polyanions (e.g., (PS 3 ) n n– chains and P 2 S 6 4– ). Overall, this work demonstrates how ssNMR and nPDF can be used to draw key structure/function correlations for solid-state superionic conductors.
36 MATERIALS SCIENCE↗
Quantitative 14 N NMR with Monte Carlo Uncertainty Analysis of Nitrate/Nitrite in Alkaline Nuclear Waste
While monitoring of nitrate and nitrite concentrations is important for managing corrosion in nuclear waste systems, existing analytical methods are hindered by turbidity, spectral interference, and delays from sample handling. Here, we demonstrate quantitative 14 N nuclear magnetic resonance (qNMR) spectroscopy as a direct, matrix-tolerant approach for nitrate and nitrite detection at natural abundance. Monte Carlo resampling was integrated into the workflow to quantify random error, establish precision–time tradeoffs, and separate noise-limited uncertainty from systematic bias arising from shimming, transmitter offset, or excitation pulse conditions. Quantification of nitrate and nitrite were validated in controlled alkaline matrix challenges and in 18-component Hanford-type simulants. These results establish 14 N qNMR as a practical, uncertainty-bounded tool for monitoring redox-active nitrogen species in chemically complex environments and provide a generalizable framework for quantitative analysis of quadrupolar nuclei.
Graham, Trent R. [Pacific Northwest National Labor↗
NMR Relaxometry and Diffusometry Analysis of Dynamics in Ionic Liquids and Ionogels for Use in Lithium-Ion Batteries
Solvation and transport properties of methlyviologen dichloride in mixtures of choline chloride (ChCl) and ethylene glycol (EG) including the deep eutectic solvent (DES) ethaline were studied through physical property measurements, cyclic voltammetry, and Raman spectroscopy. The transport properties of the solvate structures in ethaline and ChCl:EG mixtures were compared to a well-studied ionic liquid (IL), 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [PYR13][TFSI] through the lens of hole theory. Exchanging the chloride anion of ethaline with bis(trifuoromethylsufonyl)imide) anion, [TFSI], is found to increase the fluidity of the solvent and promoted stronger solute-solvent interactions. Raman spectroscopy shows that methylviologen is solvated by EG in solutions with ChTFSI but interstitially accommodated in void spaces in both ChCl solutions and [PYR13][TFSI]. Complex solvents such as DESs are regarded as “designer solvents” and we demonstrate that the physical properties and solvation characteristics of these fluids can be varied by anion exchange of hydrogen bond acceptors.
25 ENERGY STORAGE↗
Design and optimization of THz coupling in zirconia MAS rotors for dynamic nuclear polarization NMR
Not Available
Biochemistry & Molecular Biology↗
The S solubility of Cr and Al containing simulated low-activity waste glass
Here, the presence of sulfur-containing molten salt phases during vitrification is a particular problem which can be detrimental to the melter. Borosilicate compositions were designed to explore both the effects of a fixed amount of Cr, as Cr 2 O 3 or Na 2 CrO 4 , and the impact of Al 2 O 3 , on sulfur solubility as determined by progressively adding elemental S. The NABS series (with Al 2 O 3 ) has a higher SO 3 solubility of ~3.5 mol% while the NBS series (without Al 2 O 3 ) has a SO 3 solubility of ~2 mol%. Crystalline Cr 2 O 3 formed in the NABS series upon the addition of S but is not present in the NBS series. At the highest S addition, a separate salt phase always forms, and was identified as Na 2 (S,Cr)O 4 via electron dispersive spectroscopy, ultraviolet-visible spectroscopy, x-ray diffraction, and thermal analysis. Magic angle spinning nuclear magnetic resonance identified no change in the B coordination in either series as S is added, suggesting that the Na is scavenged from other locations, such as the Si sites, to charge compensate sulfate, whether in the glass or in the salt. The Cr precursor identity did not affect the observed overall behavior regarding sulfur, but did impact Cr redox as identified with Raman spectroscopy.
36 MATERIALS SCIENCE↗
Relativistic DFT Calculations of Cadmium and Selenium Solid-State NMR Spectra of CdSe Nanocrystal Surfaces
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Elucidating molecular level interfacial interactions between a de novo protein and nucleated calcite with solid-state NMR
Biomineralization is the process by which organisms use biomolecules to produce hierarchically structured organic–inorganic composites. Using biology as inspiration, a protein construct (FD31) was previously designed to accelerate formation of nano-calcite with an unconventional {110} face. Here, to understand the molecular interactions essential for protein aided calcite nucleation, solid-state nuclear magnetic resonance (ssNMR) spectroscopy was used in this work to characterize the FD31–calcite interface at the atomic level. Glutamic acid side chains designed to interact directly with calcium ions on the surface were found to have dynamics on the sub-millisecond timescale, indicating possible interactions between the protein and surface waters that were not included in the original model. Dipolar ssNMR recoupling techniques also showed that the protein backbone is ∼2 Å closer to the surface than in the original docking model. Refined molecular simulations were done in the presence of explicit waters, which resulted in the protein backbone closer to the surface than in the original docking structure, providing better agreement with experiment and highlighting the important role played by water in FD31–calcite interactions. While this work provides the first experimental confirmation that FD31 interactions with calcite are localized to the surface of the protein designed to serve as a template, these studies do indicate a more dynamic binding and closer binding mode between FD31 and the nucleated surface than originally proposed. In all, this enhanced molecular insight into the FD31–calcite interface has advanced our fundamental understanding of the atomic interactions at the organic–inorganic interface and will aid in the design of biological templates for the nucleation of inorganic crystals.
Close, Emily G. S. [Pacific Northwest National Lab↗
DataSet for Elucidating molecular level interfacial interactions between a de novo protein and nucleated calcite with solid-state NMR
Biomineralization is the process by which organisms use biomolecules to produce hierarchically structured organic-inorganic composites. Using biology as inspiration, a protein construct (FD31) was previously designed to accelerate formation of nano-calcite with an unconventional {110} face. To understand the molecular interactions essential for protein aided calcite nucleation, solid-state nuclear magnetic resonance (ssNMR) spectroscopy was used in this work to characterize the FD31-calcite interface at the atomic level. Glutamic acid side chains designed to interact directly with calcium ions on the surface were found to have dynamics on the sub-millisecond timescale, indicating possible interactions between the protein and surface waters that were not included in the original model. Dipolar ssNMR recoupling techniques also showed that the protein backbone is ~2 Å closer to the surface than in the original docking model. Refined molecular simulations were done in the presence of explicit waters, which resulted in the protein backbone closer to the surface than in the original docking structure, providing better agreement with experiment and highlighting the important role played by water in FD31-calcite interactions. These studies provide the first experimental evidence to confirm that FD31 interactions with calcite are localized to the surface of the protein designed to serve as a template. However, these studies do indicate a more dynamic binding and closer binding mode between FD31 and the nucleated surface than originally proposed. In all, this enhanced molecular insight into the FD31-calcite interface has advanced our fundamental understanding of the atomic interactions at the organic-inorganic interface and will aid in the design of biological templates for the nucleation of inorganic crystals.
Saccuzzo Close, Emily Grace [Pacific Northwest Nat↗
Resolving Chemical and Spatial Heterogeneities at Complex Electrochemical Interfaces in Li-Ion Batteries
The high specific capacities of Ni-rich transition metal oxides have garnered immense interest for improving the energy density of Li-ion batteries (LIBs). Despite the potential of these materials, Ni-rich cathodes suffer from interfacial instabilities that lead to crystallographic rearrangement of the active material surface as well as the formation of a cathode electrolyte interphase (CEI) layer on the composite during electrochemical cycling. While changes in crystallographic structure can be detected with diffraction-based methods, probing the chemistry of the disordered, heterogeneous CEI layer is challenging. In this work, we use a combination of ex situ solid-state nuclear magnetic resonance (SSNMR) spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information, on the nanometer length scale, on the CEI deposited on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite cathode films. XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13 C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, here we find that LiF, Li 2 CO 3 , and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1 H and 19 F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially-resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films.
36 MATERIALS SCIENCE↗