Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “N”

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.

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

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Single-Step Conversion of Ethanol to n-Butene over Ag-ZrO2/SiO2 Catalysts

Ethanol is a promising platform molecule for production of a variety of fuels and chemicals. Of particular interest is producing middle distillate fuels (i.e., jet and diesel blendstock) from renewable ethanol feedstock. State-of-the-art alcohol-to-jet technology requires multiple process steps based on catalytic dehydration of ethanol to form ethylene, followed by sometimes a multi-step oligomerization, and then hydrotreatment and distillation. Here we report on a new catalytic route in which ethanol is directly converted to n-butene (1- and 2-butene mixtures) over Ag-ZrO2/SBA-16, thus offering the potential for a reduction in the number of required processing steps versus conventional alcohol-to-jet technology. This catalyst system provides the balanced metal and Lewis acid sites required to selectively facilitate a cascading sequence of reactions that includes dehydrogenation, aldol condensation, Meerwein–Ponndorf–Verley reduction, dehydration, and hydrogenation. High conversion and selectivity toward either n-butene or 1,3-butadiene is achieved by tuning the hydrogen feed partial pressure and other process/catalyst parameters. With sufficient hydrogen partial pressure 1,3-butadiene is completely and selectively hydrogenated to form n-butene. The reaction mechanism was elucidated through operando-nuclear magnetic resonance investigations coupled with reactivity measurements. Combined experimental-computational investigation reveals how changes in silver and zirconium composition and the silver oxidation state affects reactivity under controlled hydrogen partial pressures and after prolonged run times. Finally, catalyst effectiveness also was demonstrated when using wet ethanol feed, thus highlighting process flexibility in terms of feedstock purity requirements. This work was financially supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, and was performed at the Pacific Northwest National Laboratory (PNNL) under Contract No. DE-AC05-76RL01830 and the National Renewable Energy Laboratory under Contract No. DE-AC36- 08GO28308. Part of the work conducted by S. A. Akhade was performed under the auspices of the U.S. DOE at Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344. This work was partly supported through the PNNL-WSU Distinguished Graduate Research Program for ADW. NMR and XPS experiments were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research

Dagle, Vanessa↗
DOE OSTI2021

Synthesis and Characterization of Divalent Samarium and Thulium N , N -Dimethylaminodiboranates

Here, the syntheses and molecular structures of new Sm II and Tm II N,N-dimethylaminodiboranate (DMADB) complexes are described. Treating SmI 2 (THF) 2 with Na(H 3 BNMe 2 BH 3 ) in THF results in the formation of Sm(H 3 BNMe 2 BH 3 ) 2 (THF) 3 (1), which can be readily converted to Sm(H 3 BNMe 2 BH 3 ) 2 (DME) 2 (DME = 1,2-dimethoxyethane) or Sm(H 3 BNMe 2 BH 3 ) 2 (diglyme) by exchange with the corresponding ether. We also show that Sm(H 3 BNMe 2 BH 3 ) 2 (THF) 3 can be prepared by reduction of the SmIII compound Sm(H 3 BNMe 2 BH 3 ) 3 (THF) with KC 8 and that addition of 18-crown-6 to this reaction mixture results in the formation of the Sm II compound Sm(H 3 BNMe 2 BH 3 ) 2 (18-crown-6). In a similar fashion, two new Tm II complexes have been synthesized: treatment of TmI 2 in THF with Na(H 3 BNMe 2 BH 3 ) results in the formation of Tm(H 3 BNMe 2 BH 3 ) 2 (THF) 2 and Tm(H 3 BNMe 2 BH 3 ) 2 (THF) 3 , which form a cocrystal. IR data and elemental analyses are reported for all the new compounds, as are their crystal structures. 1 H and 11 B NMR data are provided where available.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ab Initio Study of Vibronic and Magnetic 5f-to-5f and Dipole-Allowed 5f-to-6d and Charge-Transfer Transitions in [UX 6 ] n – (X = Cl, Br; n = 1, 2)

The absorption spectra of the octahedral [UX 6 ] n– (X = Cl, Br; n = 1, 2) complexes in the near-infrared (NIR) and UV–vis spectral regions were studied theoretically, using a relativistic restricted active space second-order perturbation theory (RASPT2) wavefunction framework, with the spin–orbit (SO) coupling treated by state interaction, in conjunction with Kohn–Sham density functional theory calculations for determining the vibrational normal modes. The electric-dipole-allowed ligand-to-metal charge-transfer (LMCT) and 5f-to-6d transitions, and the electric-dipole-forbidden 5f-to-5f ligand field (LF) transitions, are thereby obtained within the same theoretical framework. For the 5f-to-5f LF transitions, the observed absorption intensity is mostly due to vibronic coupling with low-energy electric-dipole-allowed transitions, but in some cases, the magnetic dipole intensity of the purely electronic transition has comparable intensity to the vibronic transitions. Here, experimental LF spectra of 5f 2 open-shell systems have been reported decades back, but ab initio calculations of their vibronic intensity have not yet been reported in the literature. Although the LF spectra for the 5f 2 systems can be assigned in detail, based on the calculations, the spectra are very complex and the underlying electronic states are strongly multiconfigurational. Therefore, the usefulness of the LF spectra beyond serving as a “fingerprint” of the LF and the metal oxidation state appears to be limited.

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

Fantastic n = 4: Ce5Co4+xGe13−ySny of the A n +1M n X3 n +1 homologous series

Ce-based intermetallics are of interest due to the potential to study the interplay of localized magnetic moments and conduction electrons. Our work on Ce-based germanides led to the identification of a new homologous series An+1MnX3n+1 (A = rare earth, M = transition metal, X = tetrels, and n = 1–6). This work presents the single-crystal growth, structure determination, and anisotropic magnetic properties of the n = 4 member of the Cen+1ConGe3n+1 homologous series. Ce5Co4+xGe13−ySny consists of three Ce sites, three Co sites, seven Ge sites, and two Sn sites, and the crystal structure is best modeled in the orthorhombic space group Cmmm where a = 4.3031(8) Å, b = 45.608(13) Å, and c = 4.3264(8) Å, which is in close agreement with the previously reported Sn-free analog where a = 4.265(1) Å, b = 45.175(9) Å, and c = 4.293(3) Å. Anisotropic magnetic measurements show Kondo-like behavior and three magnetic transitions at 6, 4.9, and 2.4 K for Ce5Co4+xGe13−ySny.

Weiland, Ashley (ORCID:0000000171983559)↗
DOE OSTI2022

Synthesis and Characterization of Homoleptic Rare Earth Nitrato Complexes with the Quaternary Ammonium Cations Et 4 N + and n Pr 4 N +

Two periodic series of homoleptic rare earth nitrato com plexes, [R 4 N] x [M(NO 3 ) y ](M = La-Nd, Sm-Lu, Y); R = Et, $n$ Pr; x = 2-3; y = 5-6) have been synthesized, and charac terized by single crystal X-ray diffraction, IR and Raman spectroscopy, comparing the solid state speciation of the nitrate ions as a function of lanthanide ion and quarternary ammonium cation. The series of the form [Et 4 N] 3 [Ln(NO 3 ) 6 ] crystallizes in the rhombohedral space group $R$$\bar{3}$, as a twelve-coordinate hexanitrato complex [Et 4 N] 3 [Ln(NO 3 ) 6 ] with cocrystallized HNO 3 for La, Pr, and Nd. For Ce, a distinct orthorhombic phase retaining the same formula, [Et 4 N] 3 [Ce(NO 3 ) 6 ] is isolated in the absence of HNO 3 to prevent oxidation of the Ce(III) to Ce(IV) in nitric acid. A ten-coordinate pentanitrato complex, [Et 4 N] 2 [Ln(NO 3 ) 5 ], in monoclinic symmetry forms for the remainder of the series, and for Y(III). The entire series crystallized in the presence of [ $n$ Pr 4 N] + counterions forms a pentanitrato complex [ $n$ Pr 4 N] 2 [M(NO 3 ) 5 ] in the orthorhombic space group, $Pccn$. In conclusion, analysis of trends in the structural and spectroscopic characteristics of these series reveal insight into the structure directing influences of both the lanthanide contraction and the quarternary ammonium cations.

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

Correlated $\ n-γ$ angular distributions from the $\ Q$ = 4.4398 MeV 12 C ($\ n, n' γ$) reaction for incident neutron energies from 6.5 MeV to 16.5 MeV

Neutron scattering cross sections and angular distributions represent one of the most glaring sources of uncertainty in calculations of nuclear systems. Even simple nuclei like 12 C show indications of errors in nuclear databases for scattering reactions. Measurements of inelastic neutron scattering have historically measured either the scattered neutrons or the nuclear deexcitation $\ γ$ emission. Only a very small number of experiments attempted correlated measurements of both the neutron and $\ γ$ data simultaneously, even though these $\ n-γ$ correlations could be essential for understanding particle transport in nuclear systems. In this work we describe a measurement of the $\ n, γ$, and correlated $\ n-γ$ angular distributions from the $\ Q$ = 4.4398 MeV 12 C ($\ n, n'γ$) reaction in a single experiment using an EJ-309 liquid scintillator detector array with wide angular coverage, and with a continuous incident neutron energy range from 6.5 to 16.5 MeV. We also provide a thorough covariance description of these results, including normalization of the probability distribution. While the measured n distributions agree well with the relatively large number of available literature measurements, there are comparatively very few measurements of the γ distributions from this reaction. However, our data support the presence of a nonzero α 4 Legendre polynomial component of the γ angular distribution suggested in past measurements, which is currently not incorporated in the ENDF/B-VIII.0 library despite the use of these same literature data for evaluation of the 12 C ($\ n, n'γ$) cross section. The correlated $\ n-γ$ distribution measurements are limited to three measurements at incident neutron energies near 14 MeV. Our results do not generally agree with any of these literature measurements. We observe clear indications of significant changes in the $\ n$ distribution for specific $\ γ$-detection angles and vice versa especially near thresholds for other reaction channels, which shows the potential for significant bias in experiments that, for example, tag on inelastic scattering using a single or small number of $\ γ$ -detection angles and could impact particle transport calculations.

6 ≤ A ≤ 19↗
DOE OSTI2021

Fission TPC FY2020 Report (Mid Q2 FY2021): Preliminary 235 U(n,f)/ 6 Li(n,t)α Cross Section Ratio Analysis & Update on the 239 Pu(n,f) Data Collection

Fission TPC L2 Milestone Description: The fission TPC experimental campaign is in its final stages of collecting high precision (n,f) cross section data aimed at improving our understanding of the 239 Pu fission process. During FY 2019 235 U(n,f)/ 6 Li(n,t) ratio data collection began at WNR/LANSCE. This data is the first step in demonstrating the efficacy of 6 Li(n,t) as a diagnostic standard for a 239 Pu(n,f) ratio measurement. In FY 2020 and FY2021, the NIFFTE Collaboration will analyze 235 U(n,f)/ 6 Li(n,t) data already collected to establish this technique in preparation for 239 Pu(n,f)/ 6 Li(n,t) ratio data. Additionally, the ability to vapor deposit 239 Pu was developed in 2019, greatly improving target quality. As access to experimental facilities allows, 239 Pu/ 235 U and 239 Pu/ 6 Li data will be collected to provide new inputs for evaluation of the 239 Pu(n,f) cross section.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Mesoporous 3D/2D NiCoP/g-C 3 N 4 Heterostructure with Dual Co–N and Ni–N Bonding States for Boosting Photocatalytic H 2 Production Activity and Stability

The mesoporous 3D/2D NiCoP/g-C 3 N 4 heterostructure is fabricated by embedding NiCoP nanoclusters on the surfaces of g-C 3 N 4 nanosheets, which exhibit more outstanding photocatalytic H 2 production activity than g-C 3 N 4 modified with Pt and other similar phosphides. The highest H 2 production rate over NiCoP/g-C 3 N 4 heterostructures reaches up to about 2.27 times than that of Pt/g-C 3 N 4 under visible light, and meanwhile, the NiCoP/g-C 3 N 4 heterostructure can maintain a continuously stable H 2 production rate during long cyclic running of 15 times in a total of 60 h. Here, the structure and properties investigations reveal that the splendid H 2 production activity and stability derive from the formed dual Co–N and Ni–N bonding states between 3D NiCoP nanoclusters and 2D g-C 3 N 4 nanosheets that can efficiently facilitate the transfer and separation of charge carriers and improve the interaction at heterointerfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Observations of the Cabibbo-Suppressed decays $Λ^{+}_{c}$ → $\mathcal{n}$$π$ + $π$ 0 , $\mathcal{n}$$π$ + $π$ - $π$ + and the Cabibbo-Favored decay $Λ^{+}_{c}$ → $\mathcal{n}$$K$ - $π$ + $π$ + *

Using electron-positron annihilation data samples corresponding to an integrated luminosity of 4.5 fb -1 , collected by the BESIII detector in the energy region between $4599.53$ $MeV$ and $4698.82$ $MeV$ we report the first observations of the Cabibbo-suppressed decays $Λ^{+}_{c}$ → $\mathcal{n}$$π$ + $π$ 0 , $Λ^{+}_{c}$ → $\mathcal{n}$$π$ + $π$ - $π$ + , and the Cabibbo-favored decay $Λ^{+}_{c}$ → $\mathcal{n}$$K$ - $π$ + $π$ + with statistical significances of $7.9σ$, $7.8σ$, and Misplaced &, respectively. The branching fractions of these decays are measured to be $\mathcal{B}$($Λ^{+}_{c}$ → $\mathcal{n}$$π$ + $π$ 0 ) = ($0.64 ± 0.09 ± 0.02$)%, $\mathcal{B}$($Λ^{+}_{c}$ → $\mathcal{n}$$π$ + $π$ - $π$ + ) = ($0.45 ± 0.07 ± 0.03$)%, and $\mathcal{B}$ $Λ^{+}_{c}$ → $\mathcal{n}$$K$ - $π$ + $π$ + ) = ($1.90 ± 0.08 ± 0.09$)% where the first uncertainties are statistical and the second are systematic. We find that the branching fraction of the decay $Λ^{+}_{c}$ → $\mathcal{n}$$π$ + $π$ 0 is about one order of magnitude higher than that of $Λ^{+}_{c}$ → $\mathcal{n}$ $π$ + .

$Λ^{+}_{c}$ baryon↗
DOE OSTI2022

Homologous Alkali Metal Copper Rare-Earth Chalcogenides A 2 Cu 2 n Ln 4 Q 7+ n ( n = 1, 2, 3)

Twenty-seven new members of the A 2 Cu 2n Ln 4 Q 7+n (A = Cs, Rb; Ln = La-Nd, Sm, Gd-Yb; Q = S, Se) homologous series were synthesized in one of three structural types (indicated by n = 1, 2, 3). All the compounds contained 3D frameworks with alkali-metal-containing tunnels. For each increment in n, one Cu 2 Q was added, which was incorporated into the framework as an edge-sharing tetrahedron by replacing a square planar chalcogenide site. High-throughput DFT calculations predicted many of the phases to be thermodynamically stable. These predictions were compared with the synthesis results for the phases formed in each composition space. In the syntheses, heavier lanthanides showed a preference to start forming the n = 3 ACu 3 Ln 2 Q 5 , which is consistent with the predictions. RbCuNd 2 Se 4 and RbCuTb 2 Se 4 were found to be thermally stable under vacuum at temperatures up to 1000 °C. Optical measurements revealed band gaps of 1.55(5) and 1.62(5) eV for CsCuCe 2 Se 4 and RbCuTb 2 Se 4 , respectively, and a work function of 4.83(5) eV for CsCuPr 2 Se 4 . Additionally, some n = 3 ACu 3 Ln 2 Qs compounds exhibit a negative phonon mode because of a copper atom coordination, which may distort to a trigonal planar geometry at sufficiently low temperatures. The dynamic instabilities and the predicted distortion in the copper tetrahedra for the n = 3 ACu 3 Ln 2 Q 5 compounds were found to have a linear relationship with the atomic number of the lanthanides and the electronegativity of the lanthanides. In conclusion, the A 2 Cu 2 n Ln 4 Q 7+n compounds can potentially find application as high-temperature thermoelectric materials and other semiconductors.

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

Measurement of the cross section of the Q=4.4398 MeV 12 C (n, n'γ) reaction from threshold to 16.5 MeV using γ and correlated n–γ detection

The Q=4.4398 MeV 12 C (n, n'γ) cross section was measured using a white incident neutron source through the detection of γ rays only and n–γ coincidences using a segmented liquid scintillator detector array. While the n–γ technique utilized here is more generally applicable to a wide variety of neutron scattering measurements, the γ-only technique was successfully applied to this reaction to exploit the precise time resolution and high efficiency of this detection system to yield results with unprecedented statistical precision and total uncertainties < 2 % from reaction threshold up to 16 MeV incident neutron energy, clearly resolving many features in this reaction that were previously not well known. The γ-only and n–γ results are consistent with each other for the majority of the incident energy range covered in this paper, thereby lending validation to the n–γ technique for future measurements, though significant disagreements are observed between both results and with the ENDF/B-VIII.0 nuclear data evaluation. These differences are particularly noticeable in the recently evaluated energy range below 6.5 MeV, and also near 14 MeV where a “sawtooth”-like feature is observed similar to that in other 12 C+n reaction channels. Finally, both γ-only and n–γ results are presented here with thorough covariance derivations.

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

Synthesis and Purity Specifications for N,N'-Dicyclohexyl-N"-(10-nonadecyl)guanidinium Chloride for Use in Next Generation Caustic-Side Solvent Extraction

This report describes a synthesis procedure for the alkylguanidine, N,N'-dicyclohexyl-N"-(10-nonadecyl)guanidine (DCNDG), which has been identified as a promising candidate for replacing the less stable N,N',N"-tri(3,7-dimethyloctyl)guanidine (TiDG) suppressor in the Next Generation Caustic-Side Solvent Extraction (NG-CSSX) process. A verified procedure for the preparation of the amine used in this synthesis is also included. In addition, requirements for the purity of DCNDG to be utilized in the NG-CSSX process without adverse effect on the Cs + extraction and stripping are given.

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

Towards a Deeper Fundamental Understanding of (Al,Sc)N Ferroelectric Nitrides

Density functional theory (DFT) calculations, within the virtual crystal alloy approximation, are performed, along with the development of a Landau-type model employing a symmetry-allowed analytical expression of the internal energy and having parameters determined from first principles, to investigate properties and energetics of Al1-xScxN ferroelectric nitrides in their hexagonal forms. These DFT computations and this model predict the existence of two different types of minima, namely, the fourfold-coordinated wurtzite (WZ) polar structure and a five-fold coordinated paraelectric hexagonal phase (denoted as H5), for any Sc composition up to 40%. The H5 minimum progressively becomes the lowest-energy state within hexagonal symmetry as the Sc concentration increases from 0 to 0.4. Furthermore, the model points to several key findings. Examples include the crucial role of the coupling between polarization and strains to create the WZ minimum, in addition to polar and elastic energies, and that the origin of the H5 state overcoming the WZ phase as the global minimum within hexagonal symmetry when increasing the Sc composition mostly lies in the compositional dependency of only two parameters-one linked to the polarization and another one being purely elastic in nature. Other examples are that forcing Al1-xScxN systems to have no or a weak change in lattice parameters when heating them allows us to reproduce their finite-temperature polar properties well and that a value of the axial ratio close to that of the ideal WZ structure implies a large polarization at low temperatures but not necessarily at high temperatures because of the ordered-disordered character of the temperature-induced formation of the WZ state. Such findings should allow for a better fundamental understanding of (Al,Sc)N ferroelectric nitrides, which may be used to design efficient devices having, e.g., low operating voltages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Reduktive Eliminierung von Tetraalkylcupraten [Me n Cu(CF 3 ) 4− n ] − ( n =0–4): jenseits einfacher Oxidationsstufen

Abstract In den letzten Jahren haben Organocuprate im Allgemeinen und der Komplex [Cu(CF 3 ) 4 ] − im Besonderen wegen ihrer elektronischen Strukturen erhebliches Interesse auf sich gezogen. Obwohl der Reaktivität dieser Spezies in diesem Zusammenhang eine Schlüsselrolle zukommen dürfte, fand dieser Aspekt bisher nur wenig Beachtung. Wir untersuchen hier systematisch die Reihe der Tetraalkylcuprate [Me n Cu(CF 3 ) 4− n ] − und ihre Gasphasenreaktivität, die sowohl konzertierte reduktive Eliminierungen als auch Radikalverluste umfasst. Mit Hilfe quantenchemischer Rechnungen charakterisieren wir die elektronischen Strukturen der Komplexe und zeigen, wie sie mit der Reaktivität zusammenhängen. Wir finden, dass alle Ionen [Me n Cu(CF 3 ) 4− n ] − invertierte Ligandenfelder aufweisen und dass sich die unterschiedlichen Reaktivitäten der individuellen Komplexe aus dem Zusammenspiel verschiedener Effekte ergeben.

Zimmer, Bastian↗
DOE OSTI2024

Reductive Elimination From Tetra‐Alkyl Cuprates [Me n Cu(CF 3 ) 4− n ] − ( n =0–4): Beyond Simple Oxidation States

Abstract In recent years, the electronic structures of organocuprates in general and the complex [Cu(CF 3 ) 4 ] − in particular have attracted significant interest. A possible key indicator in this context is the reactivity of these species. Nonetheless, this aspect has received only limited attention. Here, we systematically study the series of tetra‐alkyl cuprates [Me n Cu(CF 3 ) 4− n ] − and their unimolecular reactivity in the gas phase, which includes concerted formal reductive eliminations as well as radical losses. Through computational studies, we characterize the electronic structures of the complexes and show how these are connected to their reactivity. We find that all [Me n Cu(CF 3 ) 4− n ] − ions feature inverted ligand fields and that the distinct reactivity patterns of the individual complexes arise from the interplay of different effects.

Zimmer, Bastian↗