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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 1,423 records · Page 79
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Proton Diffusion in Liquid 1,2,3-Triazole Studied by Incoherent Quasi-Elastic Neutron Scattering

Improving the proton transport in polymer electrolytes impacts the performance of next-generation solid-state batteries. However, little is known about proton conductivity in nonaqueous systems due to the lack of an appropriate level of fundamental understanding. Here, we studied the proton transport in small molecules with dynamic hydrogen bonding, 1,2,3-triazole, as a model system of proton hopping in a nonaqueous environment using incoherent quasi-elastic neutron scattering. By using the jump-diffusion model, we identified the elementary jump-diffusion motion of protons at a much shorter length scale than those by nuclear magnetic resonance and impedance spectroscopy for the estimated long-range diffusion. In addition, a spatially restricted diffusive motion was observed, indicating that proton motion in 1,2,3-triazole is complex with various local correlated dynamics. In conclusion, these correlated dynamics will be important in elucidating the nature of the proton dynamics in nonaqueous systems.

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

Water-In-Glass: A Self-Supporting Inorganic Aqueous Electrolyte

Aqueous rechargeable sodium-ion batteries (ARNIBs) are emerging as cost-effective and safe candidates for large-scale energy storage applications. However, their advancement has been constrained by the narrow electrochemical stability window (ESW) of conventional aqueous electrolytes (1.23 V). Here, in this study, we present a transformative approach using an inexpensive and rapidly dissolvable inorganic glass material, water glass (W-glass), to significantly enhance the ESW and enable the development of solid-state, self-supporting aqueous film (SSA film) electrolytes. These SSA film electrolytes exhibit an extended ESW of up to 3.5 V and a conductivity of ∼10 –4 S/cm at room temperature. Structural analysis using magic-angle spinning nuclear magnetic resonance (NMR) and solution-state NMR reveals that the dissolution of W-glass in water is driven by the interdependent hydrolysis of P–O–P linkages and Na + –H + ion exchange. This work offers a cost-effective and scalable solution for advancing high-performance ARNIB technology, addressing critical barriers to commercial adoption.

Electrochemical stability window↗
DOE OSTI2016

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach is introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Factors Influencing Preferential Anion Interactions during Solvation of Multivalent Cations in Ethereal Solvents

Most multivalent secondary batteries have employed electrolytes composed of cyclic ether solvents such as tetrahydrofuran or linear glycol ether solvents (glymes) such as 1,2-dimethoxyethane (G1). A robust understanding of multivalent cation solvation tendencies in these classes of solvents provides insight into corresponding structure–property relationships which, in turn, promotes the design and discovery of improved electrolytes. In this work, our goal is to systematically address how electrolyte constituent properties, namely, ether solvent structure and dication size, direct the solvation interactions of divalent electrolytes and their resultant properties. This study utilizes pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy in conjunction with Raman spectroscopy and ionic conductivity measurements to elucidate the preferential interactions between multivalent cations, anions, and solvent molecules along with their correlated ion dynamics. These investigations incorporate two representative divalent cations (Ca 2+ and Zn 2+ ) as well as two ethereal solvent representatives from both the cyclic ether and glyme structural classes. The results reveal that anions coordinate more readily with divalent cations in cyclic ethers than in glymes. Furthermore, the coordination of the anions with Ca 2+ , i.e., contact-ion pair (CIP) formation is more pronounced than with Zn 2+ in a glyme solvent of limited chain length (G1), providing insight into cation size effects that are important for translating solvation behavior across various multivalent electrolytes. Importantly, we find that specific anion coordination is more strongly controlled by solvent structure than by salt concentration in the practical range of 0.1–0.5 M. However, simply reducing these inner-sphere inter-ionic interactions by changing solvent structure does not necessarily de-correlate ionic motion. Instead, concentration-dependent changes in molar ionic conductivity suggest that second-shell interactions, i.e., solvent separated ion pairs (SSIPs), are prevalent in these electrolytes and that the solution dielectric constant, which is increased by the presence of dipolar ion pairs, is critical for controlling these interactions. These findings thus provide a basis for understanding the physical chemistry of multivalent battery electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR

Although single-site, supported organometallic catalysts were designed with homogeneity in mind, little is strictly known about their atomic-level structure and uniformity. This is in large part due to the inability of conventional characterization tools to provide structural information with adequate resolution and range for this purpose. In this work, we show that dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (NMR) enables the measurement of distances between the surface and individual carbons, making it possible to orient complexes and molecules on surfaces. We use this approach to determine the orientation and configuration of naturally 13 C-abundant acetate and supported organoiridium(III) pincer complex, both supported on γ-Al 2 O 3 . By combining solid-state NMR and extended X-ray absorption fine structure spectroscopy (EXAFS) experiments with periodic density functional theory (DFT) calculations, we are able to determine the three-dimensional arrangement of ligands around the metal center and thereby identify the structure of the supported complex at a resolution reminiscent of that associated with single-crystal diffractometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Characteristics of Non-Fullerene Acceptor-Based Organic Photovoltaic Active Layers Using X-ray Scattering and Solid-State NMR

With the recent development of non-fullerene acceptors, power conversion efficiencies of bulk-heterojunction organic solar cells have exceeded 18%. The morphology of the BHJ active layer, including packing, ordering, orientation, and phase behavior of the donor(s) and acceptor(s), plays critical roles in determining the device performance. We characterized the morphology of active layers consisting of mixtures of a PTB7/PTB7-Th (donor) and ITIC (acceptor) using grazing incidence wide-angle X-ray scattering, resonant soft X-ray scattering, and solid-state nuclear magnetic resonance (ssNMR) to correlate the morphology with device performance. PTB7-Th/ITIC shows a better device performance than that of PTB7/ITIC due to a smaller π-πstacking distance and smaller domain size of the phase separated morphology. One of PTB7/ITIC samples, processed from mixed solvents (chlorobenzene/benzene = 1:1 by volume), shows a possible partial miscibility and smaller domain size as revealed by ssNMR T 1ρ relaxation times, which is detrimental to device performance. ssNMR results showed that ITIC could crystallize into different forms depending on processing conditions, which may have implications on the manufacturing of devices using it as an ingredient, as well as its long-term stability in service.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effective Local Geometry Descriptor for 29Si NMR Q4 Anisotropy

The nuclear shielding anisotropy, ζ, is a useful nuclear magnetic resonance (NMR) shielding tensor parameter in describing the extent of electron cloud distortion about an atom. Despite the advantages afforded by NMR in structural characterization, the relationship between ζ and local structure of an atom in high-symmetry environments, such as Si-Q 4 sites, is poorly understood. Here, we use a data-driven approach combining random forest feature ranking and the Sure Independence Screening and Sparsifying Operator (SISSO) approach to derive a simple and accurate geometric descriptor for ζ with a root-mean-squared prediction error of 6.77 ppm and an R 2 of 0.761. We then apply this descriptor to describe the local geometric distortion of zeolites Sigma-2 and silica-ZSM-5 whose chemical shift anisotropy tensor has been reported. We envision that this geometric descriptor will allow for structural description and refinement in previously difficult-to-describe materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Size-Dependent Janus-Ligand Shell Formation on PbS Quantum Dots

We studied the size-dependent Janus ligand shell formation on PbS QDs employing an X-type ligand exchange reaction between native oleate ligands and two substituted cinnamic acid ligands, trifluoromethyl- and dimethyl amino-cinnamic acid, representing electron donating and electron withdrawing ligands. The exchange reactions become significantly more favorable for both electron donating and withdrawing ligands (..delta..G becomes more negative) in the smaller QDs compared to the larger QDs likely because the ligand density is smaller on the larger QDs reducing the strength of the ligand-ligand interactions. We found that Janus-ligand shells form more readily on smaller QDs than on bigger QDs with electron donating ligands. We also observed a dependence on the QD concentration that should be considered when forming Janus-ligand shells. Two-dimensional solution nuclear magnetic resonance spectroscopy (2D-NMR) shows evidence of pronounced phase segregation between oleate and electron donating ligands on the smaller QDs consistent with the enhanced ligand-ligand interactions. This study broadens our understanding of how to construct Janus and patchy ligand shell morphologies on small QDs.

14 SOLAR ENERGY↗
DOE OSTI2022

Understanding Lithium Local Environments in LiMn 0.5 Ni 0.5 O 2 Cathodes: A DFT-Supported 6 Li Solid-State NMR Study

LiMn 0.5 Ni 0.5 O 2 has been plagued by the structural failure driven by the irreversible phase change upon subsequent cycling and the structural degradation caused by the seemingly unavoidable Li/Ni exchange. This begs for a better understanding of the correlation between lithium local structures, synthesis conditions, and overall electrochemical properties of materials. In this study, we use density functional theory (DFT) to assist experimental 6 Li solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy to understand the nature and change in lithium local structures with extended annealing times (168 vs 15 h) synthesized at 900 °C. To correlate the NMR peak changes after different synthesis conditions, we calculated the NMR spectra of representative low-energy model configurations of LiMn 0.5 Ni 0.5 O 2 composition–zigzag, row, and flower structures–as well as the influence of Ni/Mn ordering and Li/Ni exchange on each spectrum using a supercell that is large enough to allow us to consider the effect of different relative configurations of adjacent transition metal (TM) layers. The analysis based on a combination of the calculated NMR and the experimental spectra suggests that most configurations contributing to the experimental spectra are in fact composed of a blend of configurations higher in energy than the classical well-ordered ground-state structures. Further, the extended annealing of LiMn 0.5 Ni 0.5 O 2 slightly enhances Ni/Mn and Li/Mn orderings while reducing the Li/Ni mixing ratio. This study shows how DFT calculations are crucial in providing a better understanding of the experimental characterization data and therefore local environments and domain structures in oxide materials, such as Li-ion battery cathodes.

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

Halide Substitution Effects on Lithium-Ion Diffusion in Protonated Antiperovskites

Solid-state electrolytes (SSEs) for all-solid-state lithium-ion batteries are generating intense interest because these batteries can improve the safety and performance compared with devices fabricated with conventional, flammable liquid electrolytes. In these SSEs, it has been suggested that Li + ion diffusion in the grain boundaries is hindered and is a critical determinant of the overall ionic conductivity (σ). However, Li + ion diffusivities in the grain (D G ) and the grain boundary (D GB ) are difficult to determine experimentally, with few techniques capable of distinguishing the individual contributions. Here, we distinguished the D G and D GB for the protonated lithium antiperovskites (pLiAPs) SSEs: Li 2 OHCl, Li 2 OHBr, Li 2 OHF 0.1 Cl 0.9 , Li 2 OHF 0.1 Br 0.9 , and Li 2 OHCl 0.3 7Br 0.63 . The measurements were obtained directly from 7 Li pulsed-field gradient nuclear magnetic resonance (PFG-NMR) at 353 K. The 7 Li PFG-NMR echo profiles were composed of two primary components with additional secondary oscillatory components – the so-called NMR diffraction phenomenon. The length scale separating the two main components corresponds to a diffusion length of ~1.7 µm, which is thought to be the average grain size (by diameter). The short-range (≤ 1.7 µm) diffusion component associated with D G (≈10 -11 m 2 /s) varied minimally with halide substitution, while the long-range (≥ 1.7 µm) component D GB (≈10 -12 to 10 -15 m 2 /s) was highly sensitive to the substitution of halides and closely correlated with s. In addition, from the comparison of the ratio D GB /D G to D t (the Li + ion diffusion coefficient estimated from the rotational correlation time, t c ), it was determined that the contribution of D G to σ is negligible; 0.01 ~ 0.04 in the pLiAPs studied here. Finally, these insights provide fundamental understanding of the halide substitution effects on Li + ion grain versus grain boundary diffusion, and suggest that careful engineering of the grain boundaries at the microscopic level is necessary to achieve high-performance pLiAP SSEs.

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

New Insights into Nonthermal Plasma-Assisted Poly(vinyl alcohol) Depolymerization Catalyzed by TiO 2

Here, in this study, we investigated the solid residual poly(vinyl alcohol) (PVA) and TiO 2 after nonthermal air, CO 2 , and N 2 plasma depolymerization in the absence and presence of TiO 2 . Scanning electron microscopy studies showed the absence of highly viscous tar and carbonaceous residues on the surfaces of PVA and TiO 2 . In the absence of TiO 2 , PVA particles exhibited micron-sized holes on their surfaces, whereas in the presence of TiO 2 , the surface roughness of PVA particles was observed at the submicron scale. These observations suggest that TiO 2 facilitates the even distribution of nonthermal plasma at a submicron scale, leading to a more uniform depolymerization of PVA surfaces. Raman, Fourier transform infrared spectroscopy, and X-ray absorption spectroscopy showed that (i) the surface of residual PVA contains mainly ketone functional groups and less C-H bonds than the pristine PVA and (ii) further confirmed the absence of highly viscous tar and carbonaceous residues on both used TiO 2 and residual PVA. The nuclear magnetic resonance and mass spectroscopy suggested that the PVA is growing back to poly polyvinyl acetate by the esterification reaction, and the ethers are produced by the acetal reaction between PVA and aldehyde. The transmission electron microscopy and X-ray diffraction analysis indicated no major crystal structural change of the TiO 2 catalyst after the plasma reactions. This study demonstrates that nonthermal plasma-assisted depolymerization is a viable alternative to thermal depolymerization, offering the unique advantage of converting polymer wastes into gaseous small organic molecules without generating recalcitrant viscous tar and carbonaceous residues on the surfaces of the polymer and TiO 2 catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores

In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at clay–water interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water and ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Investigating Li Microstructure Formation on Li Anodes for Lithium Batteries by $In Situ$ 6 Li/ 7 Li NMR and SEM

The growth of lithium microstructures during battery cycling has, to date, prohibited the use of Li metal anodes and raises serious safety concerns even in conventional lithium-ion rechargeable batteries, particularly if they are charged at high rates. The electrochemical conditions under which these Li microstructures grow have, therefore, been investigated by in situ nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and susceptibility calculations. Lithium metal symmetric bag cells containing LiPF 6 in EC/DMC electrolytes were used. Distinct 7 Li NMR resonances were observed due to the Li metal bulk electrodes and microstructures, the changes in peak positions and intensities being monitored in situ during Li deposition. The changes in the NMR spectra, observed as a function of separator thickness and porosity (using Celgard and Whatmann glass microfiber membranes) and different applied pressures, were correlated with changes in the type of microstructure, by using SEM. Isotopically enriched 6 Li metal electrodes were used against natural abundance predominantly 7 Li metal counter electrodes to investigate radiofrequency (rf) field penetration into the Li anode and to confirm the assignment of the higher frequency peak to Li dendrites. The conclusions were supported by calculations performed to explore the effect of the different microstructures on peak position/broadening, the study showing that Li NMR spectroscopy can be used as a sensitive probe of both the amount and type of microstructure formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Integrated Molecular and Microscopic Scale Insight into Morphology and Ion Dynamics in Ca2+-Mediated Natural Organic Matter Floccs

Combined X-ray diffraction (XRD), helium ion microscopy (HeIM), and Ca-43 nuclear magnetic resonance (NMR) results provide novel insight into the nano- and microstructure of flocculated NOM; the molecular-scale interaction among natural organic matter (NOM), dissolved Ca2+ ions, and water in NOM floccs; and the effects of pH and ionic strength on these characteristics. Suwannee River humic acid (HA), fulvic acid (FA), and NOM flocculated from Ca2+ bearing solutions share similar morphological characteristics on the 100 nm to micron scales, including micron-sized equant fragments and rounded, rough areas with features on the 100 nm scale. HeIM suggests that the NOM floccs are built from a fundamental spheroidal structure that is similar to 10 nm in diameter, in agreement with published AFM and small-angle X-ray scattering results. Calcium is incorporated into these floccs at 100% relative humidity in a wide range of disordered structural environments, with basic pH leading to shorter mean Ca-O distances and lower mean coordination numbers with respect to floccs formed under acidic conditions. The NMR results show that dynamical processes involving water and Ca2+ occurring at frequencies >10(4) Hz are important for hydrated OM floccs, in agreement with published molecular dynamics simulations of OM in solution. From the NMR results, we find evidence for two Ca2+ dynamic averaging mechanisms: one related to rapid exchange (>100 kHz) between surface proximity-restricted (those within 5 angstrom of a surface) and bulk solution environments when excess Ca2+ is present in the pore solution when pore water is unfrozen and a second consisting of intermediate scale (tens of kHz) site exchange among strongly sorbed inner-sphere sites when excess Ca2+ is absent and the carboxylic and phenolic functional groups of the NOM are deprotonated.

AQUEOUS-SOLUTIONS↗
DOE OSTI2025

Influence of Ether-Functionalized Pyrrolidinium Ionic Liquids on Properties and Li + Cation Solvation in Solvate Ionic Liquids

Ionic liquids are tunable solvents composed entirely of ions that have properties desirable as electrolytes for lithium batteries such as non-flammability and a large electrochemical stability window. Solvate ionic liquids are a subclass of ionic liquids that consist of a glyme-based solvent and lithium salt in an equimolar ratio, where Li + cation-glyme solvation interactions result in ionic liquid-like properties. LiG4TFSi is a well-studied solvate ionic liquid consisting of equimolar amounts of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and tetraglyme (G4). In this work, pyrrolidinium ionic liquids with ether-functionalized side chains were synthesized containing either one ether (EO1) moiety or three ether (EO3) moieties and mixed with LiG4TFSI to form a new class of electrolyte mixtures. Their physical and transport properties, as well as ion solvation structures, were characterized by electrochemical, thermal, rheological, and spectroscopic measurements. The conductivity of the electrolyte mixture composed of EO1:LiTFSI:G4 in a 1:1:1 molar ratio is 2.54 mS/cm at 30 °C, compared to 1.53 mS/cm for LiG4TFSI, an increase of 67%. A significant decrease in the conductivity to 0.279 mS/cm is observed for the EO3:LiTFSI:G4 mixture in a 1:1:0.4 molar ratio. Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) measurements revealed that the EO1 cation diffuses significantly faster than the EO3 cation in their respective mixtures. Liquid-state 13 C NMR experiments indicate that Li + cations preferentially coordinate with tetraglyme. Li + cations do not coordinate with the EO1 cation and only coordinate with EO3 ether side chains at lower concentrations of tetraglyme. We hypothesize that the oligoether EO3 cation competes with G4 and TFSI - for lithium cation solvation in G4 deficient compositions, leading to a largely adverse effect on the mass transport properties of the electrolyte.

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

Probing surface hydrogen bonding and dynamics by natural abundance, multidimensional, 17 O DNP-NMR spectroscopy

Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR) spectroscopy is increasingly being used as a tool for the atomic-level characterization of surface sites. DNP surface-enhanced SSNMR spectroscopy of materials has, however, been limited to studying relatively receptive nuclei, and the particularly rare 17 O nuclide, which is of great interest for materials science, has not been utilized. We demonstrate that advanced 17 O SSNMR experiments can be performed on surface species at natural isotopic abundance using DNP. We use 17 O DNP surface-enhanced 2D SSNMR to measure 17 O{ 1 H} HETCOR spectra as well as dipolar oscillations on a series of thermally treated mesoporous silica nanoparticle samples having different pore diameters. These experiments allow for a nonintrusive and unambiguous characterization of hydrogen bonding and dynamics at the surface of the material; no other single experiment can give such details about the interactions at the surface. Lastly, our data show that, upon drying, strongly hydrogen-bonded surface silanols, whose motions are greatly restricted by the interaction when compared to lone silanols, are selectively dehydroxylated.

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

Precursor Ion–Ion Aggregation in the Brust–Schiffrin Synthesis of Alkanethiol Nanoparticles

Tetraoctylammonium bromide is used in the Brust-Schiffrin nanoparticle synthesis to phase-transfer chloroaurate ions from the aqueous phase to the organic phase. While it is established that the quaternary ammonium complex self-associates in the organic phase, the actual self-assembled structure is debated. We have confirmed the presence of ion-ion aggregates through quantitative 1H Nuclear Magnetic Resonance spectroscopy (NMR), pulsed field gradient, diffusion-ordered NMR (DOSY-NMR) and density functional theory (DFT) based NMR shift calculations. Tetraoctylammonium complexes (TOA-X, where X = Br, Cl, AuCl4-xBrx, AuBr4/Br and AuCl4-xBrx/Br) were investigated to measure the extraction of water into the organic phase. 1H NMR and DFT based NMR shielding calculations indicated that deshielding of water is due to hydration of the anion and not the formation of the aqueous core of a reverse micelle. DOSYNMR results were consistent with the formation of small aggregates at typical Brust-Schiffrin synthesis concentrations. The extent of aggregation correlated with the size and electronegativity of the anion and was analyzed with a modified, isodesmic, indefinite aggregation model. The substitution of bromoauric acid for chlororoauric acid at conditions emulating the Brust-Schiffrin synthesis increased the aggregation of the quaternary ammonium complex. The increase in aggregation corresponded with an increase in the size of the produced nanoparticles from 4.3 to 4.6 nm. Understanding the selfassembly and supramolecular structure of precursors in the Brust-Schiffrin synthesis will enable further refinement of models that predict the growth of noble metal nanoparticles.

Density Functional Theory↗
DOE OSTI2016

125 Te NMR and Seebeck Effect in Bi 2 Te 3 Synthesized from Stoichiometric and Te-Rich Melts

Bi 2 Te 3 is a well-known thermoelectric material and, as a new form of quantum matter, a topological insulator. Variation of local chemical composition in Bi2Te3 results in formation of several types of atomic defects, including Bi and Te vacancies and Bi and Te antisite defects; these defects can strongly affect material functionality via generation of free electrons and/or holes. Nonuniform distribution of atomic defects produces electronic inhomogeneity, which can be detected by 125 Te nuclear magnetic resonance (NMR). Here we report on 125 Te NMR and Seebeck effect (heat to electrical energy conversion) for two single crystalline samples: (#1) grown from stoichiometric composition by Bridgman technique and (#2) grown out of Te-rich, high temperature flux. The Seebeck coefficients of these samples show p- and n-type conductivity, respectively, arising from different atomic defects. 125 Te NMR spectra and spin–lattice relaxation measurements demonstrate that both Bi 2 Te 3 samples are electronically inhomogeneous at the atomic scale, which can be attributed to a different Te environment due to spatial variation of the Bi/Te ratio and formation of atomic defects. In conclusion, correlations between 125 Te NMR spectra, spin–lattice relaxation times, the Seebeck coefficients, carrier concentrations, and atomic defects are discussed. Our data demonstrate that 125 Te NMR is an effective probe to study antisite defects in Bi 2 Te 3 .

36 MATERIALS SCIENCE↗