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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Size-Matching Ligand Insertion in MOF-74 for Enhanced CO 2 Capture under Humid Conditions

Among various class of materials, metal organic frameworks (MOFs) are one of the most promising candidates for CO2 capture from flue gases. In particular, M-MOF-74, where M represents different metals, are equipped with open metal sites that can lead to very high CO2 uptake at postcombustion flue gas conditions. However, these structures are known to have poor CO2 capture performance under humid conditions as water molecules bind strongly to the unsaturated metal sites, outcompeting the CO2. In this computational study, a pore space partition strategy is employed through a symmetry-matching regulated ligand insertion within the Mg-MOF-74 and Zn-MOF-74 structures, which mitigates the deterioration effect of water. In the case of Zn-MOF-74, higher selectivity as well as larger CO2 uptake in binary mixture conditions is obtained, thereby demonstrating that reduction in the pore size of MOFs can serve as viable strategy to capture CO2 under humid postcombustion conditions.

Suh, Bong Lim↗
DOE OSTI2018

Ligand Insertion in MOF-74 as Effective Design for Oxidation of Ethane to Ethanol

We report that efficient conversion of ethane into valuable materials is important with the availability of new natural gas resources. Recently, metal–organic frameworks (MOFs) with open iron sites (i.e., Fe 0.1 Mg 1.9 -MOF-74) have been shown to be promising material for catalyzing ethane to ethanol. In this computational study, various size-matching ligands are inserted into the Fe 0.1 Mg 1.9 -MOF-74 structure to further optimize this reaction. Our density functional theory calculations show that the presence of ligands enhances the binding affinity of the oxygen atoms of N2O to the iron atoms in the framework, thereby leading to an improvement in the oxidizing process. Furthermore, the reaction pathways for the new structures show reduced enthalpy barrier in the rate-determining step in the oxidation of ethane reaction cycle compared to the original Fe 0.1 Mg 1.9 -MOF-74. In conclusion, these findings provide ways in which the performance of the Fe 0.1 Mg 1.9 -MOF-74 can be optimized for next-generation catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Investigation of Ca Insertion into α-MoO 3 Nanoparticles for High Capacity Ca-Ion Cathodes

Calcium-ion batteries (CIBs) are a promising alternative to lithium-ion batteries (LIBs) due to the low redox potential of calcium metal and high abundance of calcium compounds. Due to its layered structure, α-MoO 3 is regarded as a promising cathode host lattice. While studies have reported that α-MoO 3 can reversibly intercalate Ca ions, limited electrochemical activity has been noted, and its reaction mechanism remains unclear. Here, we re-examine Ca insertion into α-MoO 3 nanoparticles with a goal to improve reaction kinetics and clarify the storage mechanism. The α-MoO 3 electrodes demonstrated a specific capacity of 165 mA h g –1 centered near 2.7 V vs Ca 2+ /Ca, stable long-term cycling, and good rate performance at room temperature. Furthermore, this work demonstrates that, under the correct conditions, layered oxides can be a promising host material for CIBs and renews prospects for CIBs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

U–C Bond Insertion, Ring-Opening, and C–H Activation in a Uranium Bis(diisopropylamino)cyclopropenylidene (BAC) Adduct

Reaction of [U(NR 2 ) 3 ] (R = SiMe 3 ) with 1 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in Et 2 O results in the formation of [(NR 2 ) 3 U(BAC)] (1), which can be isolated in modest yields. Thermolysis of 1 in C 6 D 6 at 85 °C results in the formation of the ring-opened U(IV) product, [(NR 2 ) 2 U{N(R)(SiMe 2 CH=C(NiPr 2 )C(NiPr 2 )=CH)}] (2), which can be isolated in low yields. Mechanistic studies suggest that the formation of 2 proceeds via dissociation of BAC from 1 to regenerate [U(NR 2 ) 3 ], which converts into [U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] at the elevated temperatures. BAC then inserts into the U–C bond of [U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] to generate a cyclopropenyl intermediate, which undergoes ring opening and C–H activation to afford the final product, 2. We hypothesize that the ring-opening generates an unobserved carbene intermediate. Notably, thermolysis of a 1:1 mixture of independently prepared [U{N(R)(SiMe 2 CH 2 )}(NR 2 ) 2 ] and BAC results in clean formation of 2, providing strong support for the proposed mechanism. The formulations of both 1 and 2 were confirmed by X-ray crystallography. Finally, theoretical calculations indicate that the hypothesized uranium carbene intermediate features strong U–C bonding, potentially with some carbyne character in the electronic structure.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

Mg-Ion Battery Electrode: An Organic Solid’s Herringbone Structure Squeezed upon Mg-Ion Insertion

We report that crystalline 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), an organic solid, is highly amenable to host divalent metal ions, i.e., Mg 2+ and Ca 2+ , in aqueous electrolytes, where the van der Waals structure is intrinsically superior in hosting charge-dense ions. We observe that the divalent nature of Mg 2+ causes unique squeezing deformation of the electrode structure, where it contracts and expands in different crystallographic directions when hosting the inserted Mg-ions. This phenomenon is revealed experimentally by ex situ X-ray diffraction and transmission electron microscopy, and is investigated theoretically by first-principles calculations. Interestingly, hosting one Mg 2+ ion requires the coordination from three PTCDA molecules in adjacent columns of stacked molecules, which rotates the columns, thus reducing the (011) spacing but increasing the (021) spacing. Here, we demonstrate that a PTCDA Mg-ion electrode delivers a reversible capacity of 125 mA h g –1 , which may include a minor contribution of hydronium storage, a good rate capability by retaining 75 mA h g –1 at 500 mA g –1 (or 3.7 C), and a stable cycle life. We also report Ca 2+ storage in PTCDA, where a reversible capacity of over 80 mA h g –1 is delivered.

25 ENERGY STORAGE↗
DOE OSTI2020

A charge-density-based general cation insertion algorithm for generating new Li-ion cathode materials

Future lithium (Li) energy storage technologies, in particular solid-state configurations with a Li metal anode, opens up the possibility of using cathode materials that do not necessarily contain Li in its as-made state. To accelerate the discovery and design of such materials, we develop a general, chemically, and structurally agnostic methodology for identifying the optimal Li sites in any crystalline material. For a given crystal structure, we attempt multiple Li insertions at symmetrically in-equivalent positions by analyzing the electronic charge density obtained from first-principles density functional theory. In this report, we demonstrate the effectiveness of this procedure in successfully identifying the positions of the Li ion in well-known cathode materials using only the empty host (charged) material as guidance. Furthermore, applying the algorithm to over 2000 candidate cathode empty host materials we obtain statistics of Li site preferences to guide future developments of novel Li-ion cathode materials, particularly for solid-state applications.

25 ENERGY STORAGE↗
DOE OSTI2022

New proposed ITER divertor design using carbon insert on tungsten to mitigate ELMs and secondary radiation effects on nearby components

Abstract Building a successful device for the magnetic fusion energy production is a great challenge. ITER is an international project of the tokamak based magnetic fusion design being developed for the demonstration of the feasibility of thermonuclear technologies for future realization of successful commercial fusion energy. A key obstacle to a successful magnetic fusion energy production is however, the performance during abnormal events including plasma disruptions and edge-localized modes (ELMs). A credible reactor design must tolerate at least a few of these transient events without serious consequences such as melting of the structure. This paper investigates and compares the performance of the current ITER tokamak design during two types of transient events, i.e., ELMs occurring at normal operation and disruptions during abnormal operation. We simulated the divertor components response using our integrated 3D HEIGHTS package. The simulations include self-consistent modeling of the interaction of the released core plasma particles with the initial solid divertor material, energy deposition processes, vaporization of divertor material, secondary plasma formation and MHD evolution, incident core particles collisions and scattering from this dense secondary plasma, photon radiation of secondary plasma, and the resulting heat loads on nearby components. Our simulations showed that using a small carbon insert around the strike point can significantly reduce the overall expected damage on the tungsten dome structure, reflector plates, and prevent tungsten vaporization and its potential core plasma contamination.

47 OTHER INSTRUMENTATION↗
DOE OSTI2016

Carbon nanorings with inserted acenes: Breaking symmetry in excited state dynamics

Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation to the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Lastly, our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Synergistic enhancement of nitrogen and sulfur co-doped graphene with carbon nanospheres insertion for electrocatalytic oxygen reduction reaction

A nitrogen and sulfur co-doped graphene/carbon black (NSGCB) nanocomposite for the oxygen reduction reaction (ORR) was synthesized through a one-pot annealing of a precursor mixture containing graphene oxide, thiourea, and acidized carbon black (CB). The NSGCB showed excellent performance for the ORR with the onset and half-way potentials at 0.96 V and 0.81 V (vs. RHE), respectively. It is significantly improved over that of the catalysts derived from only graphene (0.90 V and 0.76 V) or carbon nanosphere (0.82 V and 0.74 V). The enhanced catalytic activity on the NSGCB electrode could be attributed to the synergistic effect of N/S co-doping and the enlarged interlayer space resulted from the insertion of carbon nanosphere into the graphene sheets. The four-electron selectivity and the limiting current density of the NSGCB nanocomposite are comparable to that of the commercially Pt/C catalyst. Furthermore, the NSGCB nanocomposite was superior to Pt/C in terms of long-term durability and tolerance to methanol poisoning.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Arrested α-hydride migration activates a phosphido ligand for C–H insertion

Bulky tris(carbene)borate ligands provide access to high spin iron(II) phosphido complexes. The complex PhB(MesIm) 3 FeP(H)Ph is thermally unstable, and we observed [PPh] group insertion into a C–H bond of the supporting ligand. An arrested α-hydride migration mechanism suggests increased nucleophilicity of the phosphorus atom facilitates [PPh] group transfer reactivity.

Hickey, Anne K.↗
DOE OSTI2016

Investigation of sodium insertion–extraction in olivine Na x FePO 4 (0 ≤ x ≤ 1) using first-principles calculations

Olivine NaFePO4 has recently attracted the attention of the scientific community as a promising cathode material for Na-ion batteries. In this work we combine density functional theory (DFT) calculations and high resolution synchrotron X-ray diffraction (HRXRD) experiments to study the phase stability of NaxFePO4 along the whole range of sodium compositions (0 ≤ x ≤ 1). DFT calculations reveal the existence of two intermediate structures governing the phase stability at x = 2/3 and x = 5/6. This is in contrast to isostructural LiFePO4, which is a broadly used cathode in Li-ion batteries. Na2/3FePO4 and Na5/6FePO4 ground states both align vacancies diagonally within the ab plane, coupled to a Fe2+/Fe3+ alignment. HRXRD data for NaxFePO4 (2/3 < x < 1) materials show common superstructure reflections up to x = 5/6 within the studied compositions. The computed intercalation voltage profile shows a voltage difference of 0.16 V between NaFePO4 and Na2/3FePO4 in agreement with the voltage discontinuity observed experimentally during electrochemical insertion.

Saracibar, A.↗
DOE OSTI2020

Targeted synthesis and reaction mechanism discussion of Mo 2 C based insertion-type electrodes for advanced pseudocapacitors

Mo 2 C is one of the few compounds that possess good electronic conductivity. Meanwhile, it possesses a natural 1D zigzag tunnel structure that is ideally suited for fast ion diffusion. Here, an effective approach is demonstrated for fabrication of structurally stable N-doped Mo 2 C/C nanobelts. They demonstrate high and fast energy storage ability with initial capacitances of 1139 C g -1 at 1 mV s-1, 151 C g -1 at an extremely high scan rate of 2000 mV s -1 and 208 C g -1 at a discharge current density of 200 A g -1 . After electrochemical activation of cycling, the capacity is continuously enhanced and much higher capacitances of 2523 C g -1 at 1 mV s -1 and 1403 C g -1 at 50 A g -1 are achieved after 15,000 cycles at 50 mV s -1 . Using the power law, it is evaluated that a surface-controlled capacitive process makes the main contribution to the capacity, which is over 90% when the scan rates are higher than 10 mV s -1 and still high as 73% at 1 mV s -1 . From in situ synchrotron XRD, it is found that there is a negligible change in the crystal structure and volume during charging/discharging, reflecting an insertion-type charge storage mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗