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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 901 records · Page 50
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Ultrastable actinide endohedral borospherenes

Since the discovery of the first all-boron fullerenes B 40 -/0 , metal-doped borospherenes have received extensive attention. So far, in spite of theoretical efforts on metalloborospherenes, the feasibility of actinide analogues remains minimally explored. Here we report a series of actinide borospherenes AnB n (An=U, Th; n=36, 38, 40) from extensive first-principles theory calculations. All the AnB n complexes are found to possess endohedral structures (An@B n ) as the global minima. In particular, U@B 36 (C 2h , 3 A g ) and Th@B 38 (C 2h , 3 B u ) exhibit nearly ideal endohedral borospherene structures. The C 2h U@B 36 and Th@B 38 complexes are predicted to be highly robust both thermodynamically and dynamically. In addition to the actinide size match to the cage, the covalent character of the metal-cage bonding in U@B 36 and Th@B 38 affords further stabilization. Bonding analysis indicates that the C 2h Th@B 38 exhibits 3D aromaticity with σ plus π double delocalization bonding. IN conclusion, the results demonstrate that doping with appropriate actinide atoms is promising to stabilize diverse borospherenes, and may provide routes for borospherene modification and functionalization.

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

Influence of lanthanides on spin-relaxation and spin-structure in a family of Fe 7 Ln 4 single molecule magnets

A family of isostructural undecanuclear 3d–4f coordination clusters of formula [Fe III 7 Ln III 4 O 4 (OH) 3 (tea) 2 (Htea) 3 (Piv) 7 (H 2 O) 2 (NO 3 ) 3 ], where Ln = Y (1), Gd (2), Tb (3), Dy (4); PivH ≡ pivalic acid and H 3 tea ≡ triethanolamine, was synthesised in this paper. The central Fe7 core of the coordination cluster can be described in terms of two {Fe 4 O 2 } butterfly motifs sharing a common body Fe atom. The two Fe 4 mean-planes subtend a dihedral angle of ca. 72°. The Tb (3) and Dy (4) compounds show Single Molecule Magnet (SMM) behaviour as confirmed by ac-susceptibility and μ-SQUID measurements. Furthermore, 57 Fe Mössbauer spectra of 1–4 confirm the presence of high-spin Fe III sites. The spectra of all complexes in the high temperature range (30–300 K) show broad overlapping doublets which were assigned to the body and wing-tip pairs of metal ions within the Fe 7 core. The low temperature Mössbauer spectra show dependence on the nature of the rare-earth metal as a result of its interaction with the iron sites. Finally, we observed a transition from fast (2), to intermediate (1) and very slow (frozen) (3, 4) spin fluctuation phenomena in these compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Unveiling new stable manganese based photoanode materials via theoretical high-throughput screening and experiments

Here, with the increasing energy demand, developing renewable fuel production strategies such as photoelectrocatalytic hydrogen production is critical to mitigating the global climate change. In this work, we experimentally validate a new stable and photoactive material, Mg 2 MnO 4 , from the exhaustive theoretical exploration of the chemical space of X (=Mg and Ca), Mn and O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Lignin valorization process control under feedstock uncertainty through a dynamic stochastic programming approach

The randomness introduced by reactants is an issue when processing renewable bioresources. In this paper, we apply tools from dynamic stochastic programming theory to the biochemical process. Instead of introducing extra preprocessing units, we consider the inherent randomness of the process and optimize in expectation the performance of the system. In a general setting, this is a multistage stochastic optimization problem and we investigate its approximate solution via two approaches, namely stochastic dual dynamic programming (SDDP) and the finite state, finite action Markov decision process (MDP) framework. These two methods are implemented to a case study of lignin valorization that is crucial to a cost-effective biorefinery process using biomass as the feedstock.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

The sensitivity of Cu for electrochemical carbon dioxide reduction to hydrocarbons as revealed by high throughput experiments

Electrochemical CO 2 reduction to valuable products is a centerpiece of future energy technologies that relies on identification of new catalysts. Here, we present accelerated screening of Cu bimetallic alloys, revealing remarkable sensitivity to alloy concentration that indicates the migration of alloying elements to critical sites for hydrocarbon formation.

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

A mechanistic study of cellulase adsorption onto lignin

To explore the effect of lignin composition on cellulase adsorption, here dehydrogenation polymers (DHPs) were prepared from p-glucocoumaryl alcohol/coniferin/syringin, giving rise to H-DHP, G-DHP, and S-DHP, respectively. The structures of DHPs were thoroughly characterized and compared by GPC and NMR techniques, and the Langmuir isotherm protocol was applied to determine the cellulase adsorption behaviors of these different types of DHPs. The adsorption study indicated that the binding strength between the DHPs and cellulase varied in the following order: G-DHP > H-DHP > S-DHP. The inhibition of different types of DHPs on enzymatic hydrolysis of cellulose was in the same order as the cellulase adsorption, indicating that non-productive adsorption was the main way to influence cellulase. The correlation analysis results showed a positive association between the phenolic hydroxyl group content in DHPs and their maximum adsorption capacity toward enzymes. A negative correlation between the PDI and binding strength was also observed. It was also found that the adsorbed cellulase could be desorbed and retained normal enzyme activity, and so it was presumed that DHPs and cellulase were mainly linked by physisorption such as hydrogen bonding. This study clearly showed that the composition of lignin had a great impact on cellulase, and that G-type lignin exhibited the most detrimental effect. The results could provide useful information on the mechanism of cellulase adsorption onto lignin using DHPs as lignin model compounds.

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

Correlations of the physicochemical properties of organosolv lignins from Broussonetia papyrifera with their antioxidant activities

To understand the influence of lignin characteristics on their antioxidant activities, lignins were isolated from Broussonetia papyrifera by organosolv pretreatment at different temperatures. The physicochemical features of the lignins were investigated by GPC, 31 P NMR and 2D HSQC NMR analyses. An increase of organosolv pretreatment temperature resulted in a decrease of M w and an increase of the phenolic hydroxyl group content in the isolated lignin. The lignins extracted at higher organosolv pretreatment temperature showed higher antioxidant activity according to the IC 50 determined using DPPH and ABTS. The correlations between the physicochemical properties of organosolv lignins and their antioxidant activities were studied. The contents of phenolic hydroxyl groups, especially syringyl and guaiacyl, and double bonds in the C α position had positive effects on the antioxidant activity of the lignins. Finally, on the other hand, M w and aliphatic hydroxyl groups of the lignins exhibited negative correlations with the antioxidant activity.

09 BIOMASS FUELS↗
DOE OSTI2021

First-principles studies of substituent effects on squaraine dyes

Squaraine dyes are candidates for DNA-templated excitonic interactions. This work presents substituent effects on the electronic and photophysicalproperties of squaraine dyes and a correlation between empirical Hammettconstant and those properties.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

An unprecedented quinoid–donor–acceptor strategy to boost the carrier mobilities of semiconducting polymers for organic field-effect transistors

Quinoidal–aromatic conjugated polymers hold great application potential in organic field-effect transistors (OFETs). However, the development of high mobility quinoidal–aromatic conjugated polymers still lags behind the more popular donor–acceptor (D–A) conjugated polymers, mainly owing to the lack of a rational design strategy and efficient building block. Herein, a novel quinoid–donor–acceptor (Q–D–A) strategy is demonstrated to modulate the energy-level and boost the charge carrier transport mobility of conjugated polymers as opposed to the D–A system. On the basis of this strategy, a quinoidal–aromatic conjugated polymer, namely PAQM-BT, is designed and synthesized. With the combined use of quinoid, donor and acceptor units in the backbone, the resulting Q–D–A polymer PAQM-BT displays the narrowest bandgap with the deepest-lying lowest unoccupied molecular orbital (LUMO) energy level, highest backbone coplanarity, enhanced thin-film crystallinity and smallest effective hole mass ($m^*_h$) in comparison with the corresponding D–A polymer PT3B1 and quinoid–donor (Q–D) polymer PAQM-3T. Benefitting from the more effective intra- and inter-chain charge transport, as corroborated by experiment and theoretical calculations, OFET devices based on PAQM-BT exhibit a highly boosted hole mobility of up to 5.10 cm 2 V -1 s -1 , which is one and four orders of magnitude higher than that of PAQM-3T and PT3B1, respectively, and is among the highest for quinoidal–aromatic conjugated polymers. Finally, the potent Q–D–A strategy not only allows the energy level to be modulated but also leads to effective charge carrier transport, opening up possibilities to the development of high mobility quinoidal–aromatic conjugated polymers based on a variety of quinoids, donors, and acceptors.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Benchmark relativistic delta-coupled-cluster calculations of K-edge core-ionization energies of third-row elements

Here a benchmark computational study of K-edge core-ionization energies of third-row elements using relativistic delta-coupled-cluster (ΔCC) methods and a revised core-valence separation (CVS) scheme is reported. High-level relativistic (HLR) corrections beyond the spin-free exact two-component theory in its one-electron variant (SFX2C-1e), including the contributions from two-electron picture-change effects, spin–orbit coupling, the Breit term, and quantum electrodynamics effects, have been taken into account and demonstrated to play an important role. Relativistic ΔCC calculations are shown to provide accurate results for core-ionization energies of third-row elements. The SFX2C-1e-CVS-ΔCC results augmented with HLR corrections show a maximum deviation of less than 0.5 eV with respect to experimental values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗