SEARCH · Search NASA

Results for “NUCLEAR MAGNETISM”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,279 records · Page 71

All sources NASA NTRS DOE OSTI

DOE OSTI2025

Protecting air/moisture-sensitive samples using perdeuterated paraffin wax for solid-state NMR experiments under magic-angle spinning

Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a powerful technique for materials characterization, yet its application to air- and moisture-sensitive materials is often hindered by the difficulty in maintaining an inert environment during magic-angle spinning (MAS). This is particularly true for fast-MAS rotors that do not generally provide tight seals. Herein, we present a generalizable approach employing perdeuterated paraffin waxes—n-icosane-d42 and c-dodecane-d24—as protective embedding media to analyze sensitive organometallic catalysts using SSNMR. We demonstrate that these waxes significantly slow oxidative degradation under MAS conditions. Weak background 1 H and 13 C NMR signals from the waxes are effectively suppressed using double-quantum filtration and cross-polarization techniques. In conclusion, these findings offer a robust method for expanding the scope of SSNMR to air-sensitive systems, with implications for the structural study of reactive materials and catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Proton-detected 15 N- 1 H dipolar coupling/ 1 H chemical shift correlation experiment for the measurement of NH distances in biological solids under fast MAS solid-state NMR

Measurement of distances from dipolar couplings is essential for structural characterization, refinement and validation using the solid-state nuclear magnetic resonance (ssNMR) spectroscopy. Particularly, knowledge about NH dipolar interactions in biological solids is important for understanding the hydrogen (H)-bonding interactions, molecular geometry and spin dynamics. In this regard, we have proposed a proton-detected two-dimensional (2D) 15 N- 1 H dipolar coupling/ 1 H chemical shift correlation experiment using the C-symmetry based windowless recoupling of chemical shift anisotropy (ROCSA) in combination with the DIPSHIFT pulse-based method for the measurement of short NH distances in the isotopically labeled and naturally abundant biological solids at fast magic angle spinning (MAS) rates (40–70 kHz). Our proposed method results in undistorted recoupled 15 N- 1 H dipolar coupling powder lineshapes that are free from the recoupled 1 H CSA contributions under the 15 N evolution, a feature that is essential for the measurement of NH distances with improved accuracy (± 500 Hz in terms of the NH dipolar couplings). The pulse sequence developed in the present study is also insensitive to the 1H–1H homonuclear dipolar interactions, relaxation effects owing to its constant-time implementation, and t1-noise from the fluctuations in the MAS.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2017

Synthesis and characterization of novel phosphate glass matrix nanocomposites containing polyhedral oligomeric silsesquioxane with improved properties

The preparation and characterization of novel tin fluorophosphate glass (Pglass) matrix nanocomposite materials containing nanoscale trisilanolphenyl polyhedral oligomeric silsesquioxane (POSS) prepared via classical glass synthesis was investigated here to accelerate efforts to develop novel hybrid Pglass/POSS nanocomposites with enhanced benefits in suitable diverse applications. The glass transition temperatures (T g ) of the obtained nanocomposites ranged from 121.6° to 147.6 °C to an extent that depends on the nano-POSS concentrations (≤ 10 wt% POSS) in the nanocomposites. The obtained scanning electron microscopy with energy-dispersive x-ray spectroscopy and atomic force microscopy results confirmed the homogeneous molecular level dispersion of the POSS cages in the continuous Pglass matrix of the nanocomposite. Chemical reaction (or bonding) between the constituents of the nanocomposites was confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance spectroscopy. The rheological (storage and loss modulus) and nanomechanical (elastic modulus) properties of the nanocomposites significantly improved with increasing nano-POSS concentrations up to 10 wt% POSS. The molecular dispersion of the POSS and its strong physicochemical interaction with the continuous Pglass matrix can be tailored to satisfy requirements of a number of optomechanical applications where the pure glass is not useable.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Phosphate glass matrix composites incorporating trisilanol phenyl polyhedral oligomeric silsesquioxane prepared by viscous flow sintering method with enhanced benefits

The effect of mixing and sintering processes to prepare tin fluorophosphate glass (Pglass) matrix composites incorporating trisilanol phenyl polyhedral oligomeric silsesquioxane (TSP-POSS) was investigated by comparing manual and suspension mixing, one-step and stepwise sintering processes to explore the structure dynamics and physical properties in the composites as a function of the different process conditions used. Energy Dispersive X-ray analysis confirmed optimal homogeneous dispersion of the TSP-POSS molecules in the composites prepared by the suspension method. The observed increase of glass transition temperature and the reduction of non-bridging bonds in the composites are believed to be the reason for the effective dispersion of TSP-POSS molecules in the composites. The chemical reaction between the TSP-POSS and Pglass was strongly influenced by the mixing/dispersion and sintering processes investigated. 13 C cross polarized magic angle spinning (CP MAS) solid state nuclear magnetic resonance (NMR) spectroscopy confirmed the chemical stability of the TSP-POSS during the sintering process at elevated temperatures. In addition, a chemical reaction between the TSP-POSS and Pglass was evidenced by 29 Si CP MAS NMR analysis. Here, this study will provide a better fundamental understanding of the effective dispersion mechanism of the TSP-POSS molecules in the Pglass matrix that will facilitate tailoring the physicochemical properties of the composites with addition of various small concentrations of TSP-POSS for a number of applications where the pure Pglass is not applicable due to the intrinsic properties of the Pglass.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Structure of TeO 2 glass: Results from 2D 125 Te NMR spectroscopy

Despite its chemical simplicity, a definitive description of the structure of TeO 2 glass has remained elusive due to the complexity of the Te-O coordination environment. Here, in this work we probe the Te-O coordination environment in glassy TeO 2 using 2D 125 Te isotropic-anisotropic chemical shift correlation nuclear magnetic resonance (NMR) spectroscopy. The NMR results are consistent with the presence of two Te-O environments in this glass, characterized by their distinct set of 125 Te chemical shift parameters. The dominant environment (~89%) is a distorted trigonal bipyramidal TeO 4 unit, reminiscent of that observed in crystalline γ-TeO 2 . A second, minor (~11%) component can be assigned, on the basis of its chemical shift parameters, to a TeO 3 unit. Lastly, the resulting average coordination number, nTeO, measured by 125 Te NMR (nTeO ≈ 3.9) is higher than its previously reported value obtained using neutron diffraction (nTeO ≈ 3.7).

36 MATERIALS SCIENCE↗

DOE OSTI2023

Ab initio study of the structure and properties of amorphous silicon hydride from accelerated molecular dynamics simulations

This paper presents a large-scale ab initio simulation study of amorphous silicon hydride (a-Si 1-x H x ) with an emphasis on the structure and properties of the material across a range of hydrogen concentration by combining accelerated molecular dynamics (MD) simulations with first-principles density-functional calculations. The accelerated MD scheme relied on classical metadynamics, which enabled the development of 2500+ high-quality structural models of a-Si 1-x H x , with system sizes ranging from 150 to 6000 atoms and hydrogen concentrations vary from 6 to 20 at. %. The resulting amorphous networks were found to be completely free from any coordination defects and that they all exhibited a pristine band-gap in their electronic spectrum. The microstructural properties of hydrogen distributions were examined with an emphasis on the presence of isolated and clustered environments of hydrogen atoms. The results were compared with experimental data obtained from X-ray diffraction, infrared spectroscopy and nuclear magnetic resonance studies.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Fast ionic conduction achieved through the design and synthesis of ceramic heterointerfaces

Lithium (Li) chloride and iron oxychloride (FeOCl), typically nonconductive, were combined to form a [Li 1+δ Cl] δ+ /[FeOCl] δ- heterointerface composite material (LFH), achieving ionic conductivities of >1 mS cm -1 . Analysis techniques (scanning transmission electron microscopy [STEM] and electron energy-loss spectroscopy [EELS]) indicated that the microstructure of LFH consisted of an amorphous LiCl-based shell surrounding a crystalline FeOCl-based core. Electrochemical measurements alongside solid-state 6,7 Li nuclear magnetic resonance (NMR) and molecular dynamic simulations revealed Li+ as the sole conductive species, with a diffusion barrier of ~0.25 eV. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) results further supported interstitial Li + diffusion at the heterointerface and within the LiCl phase, made possible by the heterointerface. Despite susceptibility to electronic conductivity, iron’s defects and multivalency (Fe³⁺, Fe²⁺) enable the Fe–O–Cl framework to accept Cl - , facilitating Li⁺ ionic conduction. Finally, a prototype solid-state cell (showing 97% Coulombic efficiency) demonstrated the viability of this heterointerface design for applications in energy storage.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Correlation between long range and local structural changes in Ni-rich layered materials during charge and discharge process

Ni-rich cathode materials can deliver higher energy density with a lower cost compared with other conventional layered oxide materials. However, the cycling performance of Ni-rich materials needs further improvement, and the irreversible phase transformation related to the cell failure is not fully understood yet. Although an H1-H2-H3 structural change process is revealed, a more specific explanation about the difference of these hexagonal phases is needed for deeper comprehension and further targeted modification of Ni-rich materials. In this work, the different phase transformation mechanisms of LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) and LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) are investigated by C X-ray diffraction (XRD) measurement, and the relationship between structural change and capacity degradation is discussed, showing that H3 phase can be harmful for cycling. In addition, Li-6 solid state nuclear magnetic resonance (ss-NMR) experiments are carried out for detecting the Li chemical environment at different state of charge, and the data can be associated with structural change obtained from in operando XRD results. From the analysis mentioned above, a new explanation of H1/H2/H3 is given, and a relationship between long range and local structural change has been put forward for the first time.

36 MATERIALS SCIENCE↗

DOE OSTI2019

A non-aqueous sodium hexafluorophosphate-based electrolyte degradation study: Formation and mitigation of hydrofluoric acid

Fundamental characterization of battery electrolyte is crucial for rechargeable batteries. This work reports the chemical stability of sodium hexafluorophosphate (NaPF6)-based non-aqueous electrolytes containing different solvent mixtures (e.g., cyclic and acyclic carbonates) in the presence of water for Na-ion batteries. A degradation study is conducted using NaPF 6 -based electrolytes, highlighting the effect of two electrolyte additives, 2,2,2-trifluoroethoxy-2,2,2-ethoxy phosphazene (FM2) and fluoroethylene carbonate (FEC), on degradation and cell performance of full-cell Na-ion batteries. Hydrolysis of this salt in acidic condition is particularly prone to form hydrofluoric acid (HF), and can be observed in electrolytes made with battery grade carbonate solvents (<20 ppm of water). Here, degradation mechanisms of NaPF 6 -based electrolytes are studied using liquid nuclear magnetic resonance (NMR). Noticeable degradation takes place in high purity electrolytes with the presence of moisture to form HF and organophosphates in timeframes below the current shelf-life of the Na electrolytes. FEC is not efficient to protect the electrodes from being exposed to HF. On the other hand, FM2 is revealed as a “scavenger” of HF, which helps stabilize the shelf life of electrolytes that might contain or become exposed to water. Our study underscores the importance to understanding the degradation of electrolyte and improving stability toward better shelf life for sodium ion batteries.

25 ENERGY STORAGE↗

DOE OSTI2024

Operando NMR characterization of cycled and calendar aged nanoparticulate silicon anodes for Li-ion batteries

Replacing graphite anodes with Si anodes can greatly increase the energy of current Li-ion batteries. Detailed characterization of Si lithiation reactions, SEI formation, and reversibility are therefore active areas of research. Solid-state 7 Li nuclear magnetic resonance (NMR) spectroscopy is useful for characterizing different lithium local environments within Si anodes. Here, we developed an operando NMR methodology to characterize aging of carbon-coated nanoparticulate Si anodes in pouch cells paired with Ni-rich cathodes. We observed a new lithiation mechanism in the Si nanoparticles: direct formation of over-lithiated Li 15+x Si 4 (x<0.6) phase. Furthermore, our novel operando cells maintained good performance with long-term cycle and calendar aging. Here we identified trapped lithium silicides as a major contributor to capacity fade with aging. Finally, we determined that the addition of Mg (TFSI) 2 to the electrolyte decreased the amount of trapped lithium silicides and therefore increased the capacity and capacity retention for the nanoparticulate Si used.

25 ENERGY STORAGE↗

DOE OSTI2012

Assistant template and co-template agents in modeling mesoporous silicas and post-synthesizing organofunctionalizations

Mesoporous SBA-16 silicas were synthesized through a direct methodology using the template (F127) combined with co-templates (ethanol and n-butanol), with tetraethylorthosilicate as the silica source. These ordered mesoporous silica were characterized by elemental analyses, infrared spectroscopy, solid-state nuclear magnetic resonance for {sup 13}C (CP/MAS) and {sup 29}Si (HP/DEC) nuclei, nitrogen sorption/desorption processes, small angle X-ray analyses (SAXS) and transmission electron microscopy (TEM). SAXS and TEM results confirmed the space group Im3m and cubic 3D symmetry, typical for highly ordered SBA-16. The sorption/desorption data for SBA-16 and when functionalized gave type IV isotherms, with hysteresis loop H2. Surface areas of 836; 657 and 618 m{sup 2} g{sup -1} and average pore diameters of 7.99; 8.10 and 9.85 nm, for SBA-16A, SBA-16B and SBA-16C were obtained, respectively. When functionalized the silicas presented a reduction in surface area, pore volume and pore diameter due to the pendant chains that interfere with nitrogen sorption in these measurements. The co-template ethanol favors the ordered mesopores with highest wall thicknesses. - Graphical Abstract: The mesoporous SBA-16 can be synthesized from binary (F127/TEOS) or ternary (F127/alcohol/TEOs) systems to give well-ordered mesoporous silicas. The co-templates ethanol or butanol gave the final material with highest wall thickness, mainly with ethanol. After these syntheses the pores were successfully organofunctionalized to give a good incorporation of the silylating agents. The final silicas presented of well-arranged solid characteristics as expressing by three distinct peaks, as indexed by the corresponding planes. Highlights: Black-Right-Pointing-Pointer Syntheses of mesoporous silicas by using ternary (F127/agent/TEOS) and binary (F127/TEOS) systems. Black-Right-Pointing-Pointer Use of co-templates to synthesize mesoporous silicas with larger wall thicknesses. Black-Right-Pointing-Pointer Immobilization of pendant chains inside the porous silicas. Black-Right-Pointing-Pointer Ordered mesoposous silicas as new materials for possible applications on sorption and delivering drug systems.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Hydrothermal reactions: From the synthesis of ligand to new lanthanide 3D-coordination polymers

The organic ligand 2,5-piperazinedione-1,4-diacetic acid (H{sub 2}PDA) was synthesized under hydrothermal conditions starting from the iminodiacetic acid and catalyzed by oxalic acid. The X-ray powder diffraction data indicates that the compound crystallizes in the P2{sub 1}/c monoclinic system as reported in the literature. The ligand was also characterized by elemental analysis, magnetic nuclear resonance, infrared spectroscopy and thermogravimetric analysis. Two new coordination networks based on lanthanide ions were obtained with this ligand using hydrothermal reaction. In addition to single-crystal X-ray diffraction, the compounds were characterized by infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and elemental analysis. Single-crystal XRD showed that the compounds are isostructural, crystallizing in P2{sub 1}/n monoclinic system with chemical formula [Ln(PDA){sub 1.5}(H{sub 2}O)](H{sub 2}O){sub 3} (Ln=Gd{sup 3+}(1) and Eu{sup 3+}(2)).The luminescence properties of both compounds were studied. In the compound (1), a broad emission band was observed at 479 nm, redshifted by 70 nm in comparison of the free ligand. In (2), the typical f–f transition was observed with a maximum peak at 618 nm, related with the red emission of the europium ions. Computational methods were performed to simulate the crystal structure of (2). The theoretical calculations of the intensity parameters are in good agreement with the experimental values. - Graphical abstract: Scheme of obtaining the ligand 2,5-piperazinedione-1,4-diacetic acid (H{sub 2}PDA) and two new isostructural 3D-coordination polymers [Ln(PDA){sub 1.5}(H{sub 2}O)](H{sub 2}O){sub 3} (Ln=Gd{sup 3+} and Eu{sup 3+}) by hydrothermal synthesis. Display Omitted - Highlights: • The ligand 2,5-piperazinedione-1,4-diacetic acid was synthetized using the hydrothermic method and characterized. • Two new 3D-coordination polymers with this ligand containing Gd{sup 3+} and Eu{sup 3+} ions were also obtained. • The compounds are isostructural and the typical luminescent properties were observed in both structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Structural analysis of highly porous γ-Al{sub 2}O{sub 3}

Two highly porous γ-aluminas, a commercial catalyst obtained from the calcination of boehmite and a highly mesoporous product obtained from amorphous aluminum (oxy)hydroxide via a sol–gel-based process were investigated by {sup 27}Al nuclear magnetic resonance (NMR), transmission electron microscopy (TEM), and atomic pair distribution function (PDF) analysis of synchrotron powder diffraction data. NMR data showed for both materials a distribution of tetrahedrally and octahedrally coordinated Al at a 0.30:0.70 ratio, which is typical for γ-aluminas. TEM studies revealed that rod-shaped particles with about 5 nm in thickness are the building blocks of the porous structure in both materials. These particles often extend to a length of 50 nm in the commercial catalyst and are considerably shorter in the sol–gel-based material, which has a higher surface area. Refinement of PDFs revealed the presence of a ∼1 nm scale local structure and the validity of a tetragonal average structure for both materials. This tetragonal average structure contains a substantial fraction of non-spinel octahedral Al atoms. It is argued that the presence of local structure is a general feature of γ-alumina, independent of precursor and synthesis conditions. The concentration of “non-spinel” Al atoms seems to correlate with surface properties, and increases with increasing pore size/surface area. This should have implications to the catalytic properties of porous γ-alumina. - Graphical abstract: Boehmite-derived and sol–gel synthesized porous γ-Al{sub 2}O{sub 3} possess identical structural properties, featuring a nm scale local structure and a tetragonal average structure. - Highlights: • Porous γ-Al{sub 2}O{sub 3} generally possesses a nm-scale local structure. • The tetragonal average structure contains a substantial fraction of “non-spinel” Al atoms. • The concentration of “non-spinel” Al atoms correlates with surface properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Cluster mediated conversion of amorphous Al(OH) 3 to γ-AlOOH

In this work, we report a synthetic pathway by which amorphous Al(OH) 3 is converted to γ-AlOOH through hydrothermal reaction in the presence of water at temperature T = 473 K. X-ray pair distribution function measurements reveal that the initially amorphous Al(OH) 3 possesses a locally γ-Al(OH) 3 -like structure, while nanocrystalline γ-AlOOH precipitates within 1 h of continuous hydrothermal exposure. Solid state nuclear magnetic resonance measurements show that resonant features associated with four- and five-member Al clusters persist through 20 min of hydrothermal treatment, and ultraviolet (UV) spectra mark the onset of UV-induced photoluminescent features characteristic to γ-AlOOH with 10 min of exposure, indicating a coexistence region of γ-Al(OH) 3 -like and γ-AlOOH-like amorphous species. Furthermore, powder x-ray diffraction measurements of desiccated powders reveal that the conversion process takes place in distinct, power law-defined stages with initial γ-AlOOH nucleation occurring within the first 20 min, followed by a ~ 1 h period of rapid grain coarsening and the subsequent onset of Lifshitz-Slyozov-Wagner-like coalescence.

36 MATERIALS SCIENCE↗

DOE OSTI2012

Synthesis, characterization and cation adsorption of p-aminobenzoic acid intercalated on calcium phosphate

Graphical abstract: Scanning electron microscopy photographs of calcium phosphate (a) and intercalated with p-aminobenzoic acid (b). Highlights: ► Calcium phosphate was intercalated with p-aminobenzoic acid. ► Guest molecule contains nitrogen and oxygen atoms from amine and carboxylic groups. ► These basic centers are potentially useful for cation coordination in ethanol solution. ► Crystal morphology of compounds is lamellar, it agrees with expected structural characteristics. -- Abstract: Crystalline lamellar calcium phosphate retained 4-aminobenzoic acid inside its cavity without leaching. The intense infrared bands in the 1033 and 1010 cm{sup −1} interval confirmed the presence of the phosphonate groups attached to the inorganic layer, with sharp and intense peaks in X-ray diffraction patterns, which gave basal distances of 712 and 1578 pm for the original and the intercalated compounds, respectively. Solid-state {sup 31}P nuclear magnetic resonance spectra presented only one peak for the phosphate groups attached to the main inorganic polymeric structure near −2.4 ppm. The adsorption isotherms from ethanol gave the maximum adsorption capacities of 6.44 and 3.34 mmol g{sup −1} for nickel and cobalt, respectively, which stability constant and distribution coefficient followed Co > Ni.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

The effects of cetyltrimethylammonium bromide surfactant on alumina modified zinc oxides

Highlights: • Synthesis of novel ZnO−Al{sub 2}O{sub 3} oxides in the presence of CTAB surfactant. • Determination of the structural, surface and optical properties. • Nanocrystalline, high-surface area ZnO−Al{sub 2}O{sub 3} oxides. • ZnO-Al{sub 2}O{sub 3} materials of different gap energy. - Abstract: Novel alumina modified zinc oxide materials were prepared by co-precipitation method in the presence of different amounts of cetyltrimethylammonium bromide (CTAB) surfactant. X-ray diffraction, {sup 27}Al magic-angle spinning Nuclear Magnetic Resonance Spectroscopy, and transmission electron microscopy studies evidenced formation of 10–15 nm zinc oxide nanoparticles in the presence of the small amounts of surfactant. Amorphous alumina and zinc aluminate phases of different coordination environment of Al sites were identified. An increase of surfactant concentration led to the elongation of nanoparticles and changes of the nature of hydroxyl groups. Precipitation in the high CTAB concentration conditions facilitated formation of mesoporous materials of high specific surface area. The materials were composed of very small (2–3 nm) zinc aluminate spinel nanoparticles. High concentration of CTAB induced widening of band gap energy.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Polyphosphazene polymer development for mixed matrix membranes using SIFSIX-Cu-2 i as performance enhancement filler particles

Phosphazene-based polymers were synthesized by using different pendant groups such as trifluoroethoxy (TFE), phenoxy (PHO) and octafluoropentoxy (OFP). High performance methoxyethoxyethoxy/cyclohexoxy (MEE/CH) based polyphosphazene was developed for the first time in literature using a mixed-substitution method. The structural, chemical, and thermal properties of these polymers were analyzed using several techniques such as Gel Permeation Chromatography (GPC), Thermal Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), and Nuclear Magnetic Resonance (NMR). Significant differences in gas transport properties of gases have been observed between these pendant groups because of their differences in glass transition temperature and physical interaction with CO 2 . For the first time, we report on the high performance of TFE polyphophazene based mixed matrix membranes (MMMs) using a SIFSIX-Cu-2i (SIFSIX) metal organic framework (MOF) as the filler particles. These MMMs showed a significant improvement in both CO 2 permeability and CO 2 /N 2 selectivity compared to pure TFE polyphosphazene membranes. As a result, the excellent gas transport properties of these membranes make them very promising material for carbon capture applications.

36 MATERIALS SCIENCE↗

DOE OSTI2022

13 C NMR study of amino acid salts in facilitated transport membranes for post-combustion carbon capture

Some of amino acid salts (AASs) have been demonstrated to be effective mobile carriers in facilitated transport membranes (FTMs) to achieve superior CO 2 permeance and CO 2 /N 2 selectivity for CO 2 capture from flue gas. Understandings of how the structures of different AASs affect the chemistry of the amine–CO 2 reaction are essential for the future development of more efficient AAS mobile carriers. In this study, the reaction chemistry of selected AASs with CO 2 was investigated by 13 C nuclear magnetic resonance (NMR) spectroscopy. The CO 2 loading and the distribution of major reaction products, including carbamate and bicarbonate products of each studied AAS were quantitatively analyzed. The positive correlation between the CO 2 loading of AAS (mol CO 2 /g AAS) and the CO 2 permeance of FTMs suggested that AAS with a higher CO 2 loading may improve the performance of FTMs. Our results also showed that increasing the steric hindrance of AAS could be a practical way to promote the bicarbonate reaction pathway and thus potentially increase the CO 2 loading (mol CO 2 /mol AAS). Moreover, 2-(1-piperazinyl)ethylamine (PZEA) was found to be a more effective multi-amine than piperazine (PZ) for synthesizing AASs due to the presence of more effective nitrogen sites per molecule. The superior CO 2 permeance of the PZEA-Sar membrane is also attributed to its more uniform membrane formation. As a result, the knowledge gained from this study will inform the rational design of more effective AAS carriers for CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗