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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Aqueous Sulfate Separation by Sequestration of [(SO 4 ) 2 (H 2 O) 4 ] 4− Clusters within Highly Insoluble Imine‐Linked Bis‐Guanidinium Crystals

Abstract Selective crystallization of sulfate with a simple bis‐guanidinium ligand, self‐assembled in situ from terephthalaldehyde and aminoguanidinium chloride, was employed as an effective way to separate the highly hydrophilic sulfate anion from aqueous solutions. The resulting bis‐iminoguanidinium sulfate salt has exceptionally low aqueous solubility ( K sp =2.4×10 −10 ), comparable to that of BaSO 4 . Single‐crystal X‐ray diffraction analysis showed the sulfate anions are sequestered as [(SO 4 ) 2 (H 2 O) 4 ] 4− clusters within the crystals. Variable‐temperature solubility measurements indicated the sulfate crystallization is slightly endothermic ( ΔH cryst =3.7 kJ mol −1 ), thus entropy driven. The real‐world utility of this crystallization‐based approach for sulfate separation was demonstrated by removing up to 99 % of sulfate from seawater in a single step.

Custelcean, Radu↗
DOE OSTI2024

Exploring Spin‐Orbit Effects in a [Cu 6 Tl] + Nanocluster Featuring an Uncommon Tl−H Interaction

Reaction of [CuH(PPh 3 )] 6 with 1 equiv. of Tl(OTf) results in formation of [Cu 6 TlH 6 (PPh 3 ) 6 ][OTf] ([1]OTf]), which can be isolated in good yields. Variable-temperature 1 H NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl−H orbital interaction. According to DFT, the 1 H chemical shift of the Tl-adjacent hydride ligands of [1] + includes 7.7 ppm of deshielding due to spin-orbit effects from the heavy Tl atom. In conclusion, this study provides valuable new insights into a rare class of metal hydrides, given that [1][OTf] is only the third isolable species reported to contain a Tl−H interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Rates of Ligand Exchange around the Bis-Oxalato Complex [NpO 2 (C 2 O 4 ) 2 ] 3- Measured by Using Multinuclear NMR Spectroscopy under Neutral to Semi-Alkaline Conditions [Rates of ligand exchange around the bis-oxalato complex NpO2(C2O4)23- measured using multinuclear NMR at neutral to semi-alkaline conditions]

The kinetics of ligand exchange between the free oxalate ion, C 2 O 4 2- , and the bis-oxalato Np V complex, [NpO 2 (C 2 O 4 ) 2 ] 3- , in aqueous solution are reported by using 13 C and 17 O NMR spectroscopy methods. Rates of exchange were measured in the pH regime of 6.5–9.0, at which speciation is shown to be suitably simple. Because the neptunium(V) complex is paramagnetic, the rates of ligand exchange were estimated by following the width of the 13 C and 17 O signals assigned to the free oxalate ion in solution and by applying the Swift–Connick method for measuring rates of exchange. A set of experiments were conducted in which pH and total oxalate concentration were varied, and the linear dependence of the rate on these parameters was demonstrated. Variable-temperature NMR spectroscopy was also performed to measure activation parameters of complexation. Finally, at pH<8.0, ΔH ≠ =16.9 ±4.9 kJ mol -1 and ΔS≠=-116.3 ±17.1kJ mol -1 K -1 , whereas at pH>8.0 there is almost no dependence on temperature, which is interpreted to indicate that hydrolysis is coupled to ligand exchange under these conditions.

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

Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes

Six-coordinate Mn III complexes are typically high-spin (S = 2), however, the scorpionate ligand, both in its traditional, hydridotris(pyrazolyl)borate form, Tp - and Tp* - (the latter with 3,5dimethylpyrazole substituents) and in an aryltris(carbene)borate (i.e. , N -heterocyclic carbene, NHC) form, [Ph(MeIm) 3 B] - , (MeIm = 3-methylimidazole) lead to formation of bis(scorpionate) complexes of Mn III with spin triplet ground states; three of which were investigated herein: [Tp 2 Mn]SbF 6 (1SBF 6 ), [Tp* 2 Mn]SbF 6 (2SBF 6 ), and [{Ph(MeIm) 3 B} 2 Mn]CF 3 SO 3 (3CF 3 SO 3 ). These trigonally symmetric complexes were studied experimentally by magnetic circular dichroism (MCD) spectroscopy (the propensity of 3 to oxidize to Mn IV precluded collection of useful MCD data) including variable temperatures and fields (VTVH-MCD) and computationally by ab initio CASSCF/NEVPT2 methods. These combined experimental and theoretical techniques establish the 3 A 2g electronic ground state for the three complexes, and provide information on the energy of the “conventional” high-spin excited state ( 5 E g ) and other, triplet excited states. These results show the electronic effect of pyrazole ring substituents in comparing 1 and 2. The tunability of the scorpionate ligand, even by perhaps the simplest change (from pyrazole in 1 to 3,5-dimethylpyrazole in 2) is quantitatively manifested through perturbations in ligand-field excited-state energies that impact ground-state zero-field splittings. The comparison with the NHC donor is much more dramatic. In 3, the stronger σ-donor properties of the NHC lead to a quantitatively different electronic structure, so that the lowest lying spin triplet excited state, 3 E g , is much closer in energy to the ground state than in 1 or 2. The zero-field splitting (zfs) parameters of the three complexes were calculated and in the case of 1 and 2 compare closely to experiment (lower by < 10%, < 2 cm -1 in absolute terms); for 3 the large magnitude zfs is reproduced, although there is ambiguity about its sign. The comprehensive picture obtained for these bis(scorpionate) Mn III complexes thus provides quantitative insight into the role played by the scorpionate ligand in stabilizing unusual electronic structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Elucidating structure and dynamics of crystalline α-zirconium phosphates intercalated with water and methanol by multinuclear solid-state MAS NMR: A comprehensive NMR approach

Solid-state NMR experiments on 2 H, 31 P, 13 C, and 1 H nuclei, including 31 P T 1 , 1 H T 1 , and 1 H T 1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D 2 O and/or CD 3 OD. The 13 C{ 1 H} CP MAS NMR experiment performed for compound 1-CD 3 OD (Zr (HPO 4 ) 2 .0.2CD 3 OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature 2 H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD 3 rotations around the C 3 -axis. It has been demonstrated that the intercalated species, D 2 O and CD 3 OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Here, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems.

1H↗
DOE OSTI2015

Fundamental investigations into the free‐radical copolymerization of N ‐phenylmaleimide and norbornene

ABSTRACT A fundamental investigation into the copolymerization of N ‐phenylmaleimide and norbornene via conventional free‐radical polymerization techniques was conducted. Reaction conditions were optimized for molecular weight and percent yield by tuning overall concentration and initiator loading. The copolymerization kinetics were monitored using in‐situ , variable temperature nuclear magnetic resonance and first‐order behavior was observed with respect to each monomer. Although the related copolymerization of norbornene and maleic anhydride was well‐known to proceed in a perfectly alternating manner, the copolymerization of norbornene and N ‐phenylmaleimide was found to deviate from strictly alternating copolymerization behavior, producing significant amounts of sequentially enchained N ‐phenylmaleimide units within the polymeric backbone. This deviation from perfectly alternating behavior was confirmed by analysis of individual monomer conversion rates and by measurement of monomer reactivity ratios using the Mayo–Lewis graphical analysis method. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54 , 985–991

Gmernicki, Kevin R.↗
DOE OSTI2015

Imaging of Formaldehyde Adsorption and Diffusion on TiO2(110)

Surface reactions of formaldehyde with reduced TiO2(110) surfaces have been studied using variable-temperature scanning tunneling microscopy (STM) and density functional theory (DFT). STM results show that formaldehyde preferably adsorbs on the bridging bonded oxygen (Ob) vacancy (VO) defect site. Bias-dependent STM images show that both the Ti-bound CH2O and the VO-bound CH2O are positioned between the Ob row and the Ti row. The VO-bound formaldehyde rotates at 95 K. It starts to diffuse along the Ob row as –CH2– at ~170 K and starts to diffuse along the Ti row as a molecule at ~215 K. However, the stabilities and the configurations of the Ti-bound and the VO-bound formaldehyde calculated using DFT are not in line with the experimental results. The values of diffusion barriers determined experimentally and theoretically are also different. The discrepancy between the experiment and theory indicates the presence of a complex charge distribution related to the defects.

defects↗
DOE OSTI2019

Visualizing quantum phenomena at complex oxide interfaces: An atomic view from scanning transmission electron microscopy

Complex oxide interfaces have been one of the central focuses in condensed matter physics and material science. Over the past decade, aberration corrected scanning transmission electron microscopy and spectroscopy has proven to be invaluable to visualize and understand the emerging quantum phenomena at an interface. In this paper, we briefly review some recent progress in the utilization of electron microscopy to probe interfaces. Furthermore, we discuss several important challenges for electron microscopy to advance our understanding on interface phenomena, from the perspective of variable temperature, magnetism, electron energy loss spectroscopy analysis, electronic symmetry, and defects probing.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Multi-Method Characterization of Compression Set in Fluorosilicone O-Rings

Fluorosilicone o-rings with varying levels of compression set were investigated with a variety of methods. Low field NMR experiments were able to elucidate if the sample had taken a compression set; however, this technique did not have the sensitivity to quantify the relative level of compression set of the o-ring. Furthermore, water sorption isotherms probe the interior void structure through void space occupation and while complex, the sorption isotherms indicate a systematic loss of void volume with increasing compression set. Similarly, variable temperature 129 Xe NMR experiments indicate an elimination of macroscopic void space with increasing compression. The NMR techniques, being noninvasive, have a unique ability to assess the service status of an o-ring in real time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Combinations of NIR, Raman spectroscopy and physicochemical measurements for improved monitoring of solvent extraction processes using hierarchical multivariate analysis models

The reliability of chemical processes can be greatly improved by implementing inline monitoring systems. Combining multivariate analysis with non-destructive sensors can enhance the process without interfering with the operation. Here, we present here hierarchical models using both principal component analysis and partial least square analysis developed for different chemical components representative of solvent extraction process streams. A training set of 380 samples and an external validation set of 95 samples were prepared and Near infrared and Raman spectral data as well as conductivity under variable temperature conditions were collected. The results from the models indicate that careful selection of the spectral range is important. By compressing the data through Principal Component Analysis (PCA), we lower the rank of the data set to its most dominant features while maintaining the key principal components to be used in the regression analysis. Within the studied data set, concentration of five chemical components were modeled; total nitrate (NO 3 - ), total acid (H + ), neodymium (Nd 3+ ), sodium (Na + ), and ionic strength (I.S.). The best overall model prediction for each of the species studied used a combined data set comprised of complementary techniques including NIR, Raman, and conductivity. Finally, our study shows that chemometric models are powerful but requires significant amount of carefully analyzed data to capture variations in the chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thermal energy evolution and mechanical deformation of monocrystalline yttria-stabilized zirconia nanoparticles in aerosol deposition processes

Aerosol deposition (AD) is a coating process wherein aerosol particles are impacted on a target substrate. There are fundamental differences between the AD process (cold impact), where particle translational kinetic energy is high and thermal energy is low, and thermal spray deposition (thermal impact), where translational energy is lower but thermal energy is high. To better compare cold and thermal impact effects on particles, we carried out molecular dynamics simulations using yttria-stabilized zirconia (YSZ) nanoparticles on YSZ substrates as a model system. We performed cold impact simulations at 300 K with variable impact velocity in the 500 ms –1 –1500 ms –1 range to understand how increasing translational kinetic energy affects thermal energy and mechanical evolution. We then performed thermal impact simulations at variable temperature and impact velocity, but where the total kinetic energy of the nanoparticle was equivalent to that of a 300 K, 1000 impact. In cold impact, the temperature increases in YSZ nanoparticles at a rate of 10 13 – 10 14 K s –1 , and large temperature gradients result. Conversely, in thermal impact, nanoparticle temperatures remain uniform. Furthermore, the temperature gradients during cold impact coincide with plastic deformation in nanoparticles, while with larger thermal energies, plastic deformation is reduced.

42 ENGINEERING↗
DOE OSTI2022

Enhancing methane production of anaerobic digested sewage sludge by advanced wet oxidation & steam explosion pretreatment

Anaerobic digestion (AD) of sewage sludge is associated with lowered carbon conversion efficiency due to the recalcitrance of microbial cells in the Waste Activated Sludge (WAS) from the aeration basins with 50 % of the dry weight still being present after AD. The effect of Advanced Wet Oxidation & Steam Explosion (AWOEx) pretreatment on the methane yield at variable temperatures (165–200 °C), residence time (15–45 min) and oxygen dosage (1%–10% based on VS concentration) was tested in this study. Central composite design (JMP® Pro) was used to design 19 runs of AWOEx pretreatment of dewatered digested sewage sludge (DADSS) at different operating conditions. After pretreatment the DADSS was fed to 19 bioreactors operated in semi-continues mode at 37 °C. The highest average methane yields of 183 mL/g VS and 170 mL/g VS were found for the bioreactors receiving DADSS pretreated at 165 °C with a retention time of 15 min and 10 % O2 (Condition 1), and, 182.5 °C with a retention time of 15 min and 5.5 % O2 (Condition 2). This corresponds to an increase in the methane production of 156.2 % and 140.5 % compared to the methane production from the DADSS without pretreatment.

09 BIOMASS FUELS↗
DOE OSTI2023

Oxidation rates and redox stabilization of ferrous iron in trioctahedral smectites

Iron(II)-bearing trioctahedral smectites (saponites) form during anoxic alteration of basaltic rock. They are predicted to have been widespread on the early Earth and are observed in the oceanic subsurface today. Smectite structures, including the occupancy of sites in the octahedral sheet, affect iron redox behavior but the rates and products of trioctahedral smectite oxidation have been largely unexplored to date. In this study we synthesized two Fe(II)-bearing trioctahedral smectites, one moderate (22 wt% Fe) and one high (27 wt% Fe) in iron content. We then examined the rate, extent, and products of their oxidation by dissolved oxygen, nitrite, and hydrogen peroxide. Dissolved oxygen caused partial oxidation of Fe(II) in the smectites with 14 to 43% of Fe(II) unoxidized after 20 to 30 days of exposure. The rate and extent of oxidation correlated with the dissolved oxygen concentration and the Fe(II) content of the clay. The incomplete oxidation in these experiments is consistent with the mixed-valent trioctahedral smectites observed in oxidized natural samples but contrasts with the complete reoxidation by oxygen shown by chemically- or microbially-reduced dioctahedral smectites. Oxidation of structural Fe(II) by 5 mmol L -1 nitrite was negligible for the moderate-iron smectite and yielded only ~17% oxidation after 54 days of reaction for the high-iron smectite. Hydrogen peroxide caused rapid and near-complete oxidation of both clays. Powder X-ray diffraction, variable-temperature Mössbauer spectroscopy, and extended X-ray absorption fine structure spectroscopy together detected no crystalline or short-range-ordered secondary phases and show that oxidized iron remained in the trioctahedral smectite structure. The recalcitrant Fe(II) pool in oxidized trioctahedral smectites exists in less distorted sites than Fe(II) in the initial clays. Its unreactive nature at prolonged reaction times indicates an elevated redox potential generated by the local coordination environment. Slower oxidation rates create a larger recalcitrant Fe(II) pool, suggesting kinetic competition between oxidation and a process involved in redox stabilization, such as electron exchange between octahedral iron sites or deprotonation of hydroxyl groups in the structure. The resistance to complete oxidation of trioctahedral ferrous smectites and their full retention of iron demonstrates that transitions from anoxic to oxic conditions generate mixed-valence smectites rather than a mixture of new phases. Identifying the diagenetic products of mixed-valent trioctahedral smectites may provide an indicator in the rock record of past redox cycling. In conclusion, substantial portions of structural Fe(II) in trioctahedral smectites display slow abiotic oxidation kinetics and represent potential electron donors for both microaerophilic iron oxidizing and nitrate-reducing, iron-oxidizing microorganisms in altered mafic rocks and related settings.

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

Kinetics of the methylation of a platinum(II) diimine dithiolate complex

Pt(dbbpy)(bdt) and Pt(tmphen)(bdt) (dbbpy = 4,4'-di-t-butyl-2,2'-bipyridine; tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline; bdt2- = 1,2-benzenedithiolate) are reported. Pt(dbbpy)(bdt) reacts with one equivalent of methyl iodide to give the S-methylated product, [Pt(dbbpy)(CH3bdt)]I. The reaction follows second order kinetics with a rate constant of 1.3×10 2 M-1s-1 at 311 K. The accumulated data are consistent with direct nucleophilic attack by the coordinated bdt2- ligand sulfur atom on the carbon atom of the methyl iodide. Variable-temperature experiments yield an Arrhenius activation energy of 51 ± 3 kJ/mol. Activated complex reaction theory yields an enthalpy and entropy of activation of 48 ± 2 kJ/mol and 125 ± 7 J/(mol K), respectively, consistent with an SN2 reaction mechanism. The structure of the monosulfinate adduct, Pt(dbbpy)(bdtO2), also is reported. The fluid-solution luminescence of Pt(tmphen)(bdt) is concentration dependent and characterized by a 1591 ± 41 ns lifetime and 2.6 ± 0.2% quantum yield at infinite dilution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Electronic structure and reactivity studies of a nonsymmetric one-electron oxidized Cu II bis-phenoxide complex

Here, the tetradentate mixed imino/amino phenoxide ligand (N-(3,5-di- tert -butylsalicylidene)-N'-(2-hydroxyl-3,5-di-tert-butylbenzyl))- trans -1,2-cyclohexanediamine (salalen) was complexed with Cu II , and the resulting Cu complex (2) was characterized by a number of experimental techniques and theoretical calculations. Two quasi-reversible redox processes for 2, as observed by cyclic voltammetry, demonstrated the potential stability of oxidized forms, and also the increased electron-donating ability of the salalen ligand in comparison to the salen analogue. The electronic structure of the one-electron oxidized [2] + was studied in detail, and Cu K-edge X-ray Absorption Spectroscopy (XAS) measurements confirmed a Cu II -phenoxyl radical complex in solution. Resonance Raman (rR) and variable temperature 1 H NMR studies, coupled with theoretical calculations, showed that [2 • ] + is a triplet (S = 1) Cu II -phenoxyl radical species, with localization of the radical on the more electron-rich aminophenoxide. Attempted isolation of X-ray quality crystals of [2 • ] + afforded [2H] + , with a protonated phenol bonded to Cu II , and an additional H-bonding interaction with the SbF 6 – counterion. Stoichiometric reaction of dilute solutions of [2 • ] + with benzyl alcohol showed that the complex reacts in a similar manner as the oxidized Cu II -salen analogue, and does not exhibit a substrate-binding pre-equilibrium as observed for the oxidized bis-aminophenoxide Cu II -salan derivative.

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

Magnetic structure of triangular lattice compound Tb2Ni0.90Si2.94

AlB 2 -type ternary intermetallic compound Tb 2 Ni 0.90 Si 2.94 (space group P 6=mmm, hP 3, No. 191) was reported to exhibit spin freezing behaviour of the ferromagnetic clusters present in the system below T f = 9:9 K, along with the presence of spatially limited antiferromagnetic phase. In this work, on the basis of variable temperature zero-field neutron diffraction measurements, we have shown that the antiferromagnetic phase transition occurs for the compound below T N ~13 K. Neutron diffraction study indicates ab-plane non-collinear sine-modulated antiferromagnetic ordering of the system with wave vectors of k 1 = [±1/6, ±1/6, 0] and k 2 = [±1/3, ±1/3, 0] down to 1.7 K. The weak and diffuse nature of the magnetic Bragg peaks along with limited coherence length further confirm the short-range nature of the antiferromagnetic phase in this compound.

36 MATERIALS SCIENCE↗
DOE OSTI2015

In situ ligand generation for novel Mn(II) and Ni(II) coordination polymers with disulfide ligand: Solvothermal syntheses, structures and magnetic properties

Two coordination polymers, ([Mn{sub 2}(L1){sub 2}(μ{sub 2}-H{sub 2}O)(H{sub 2}O){sub 4}]·5H{sub 2}O){sub n}1 and ([Ni(L1)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n}2 (H{sub 2}L1=2,2′-dithiobisnicotinic acid), were prepared by the solvothermal reactions of the Mn(II) or Ni(II) ions with 2-mercaptonanicotinic acid. In 1, the [Mn{sub 2}(COO){sub 4}] units are connected by the 2,2′-dithiobisnicotinic dianion to form a two-dimensional (4,4)-connected network. In 2, the adjacent Ni(II) ions are connected by the carboxyl groups of the 2,2′-dithiobisnicotinic dianion to form an one-dimensional inorganic rod-shaped chain [Ni(COO){sub 2}]{sub n}, which are further interconnected by the 2,2′-dithiobisnicotinic ligand, giving rise to a two-dimensional framework. Variable-temperature magnetic susceptibilities of 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent metal ions. - Graphical abstract: Two 2D coordination polymers were synthesized by transition-metal/in-situ oxidation of 2-mercaptonicotinic acid. The compounds pack into 2D frameworks by the carboxyl groups of 2,2′-dithiobisnicotinic dianion and exhibit overall weak antiferromagnetic coupling. - Highlights: • Two 2D coordination polymers containing 2,2′-dithiobisnicotinic dianion. • In situ oxidation and dehydro coupling reaction of 2-mercaptonbenzoic acid. • Two compounds display weak antiferromagnetic exchanges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗