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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 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Efficient Removal of Metolachlor and Bacterial Community of Biofilm in Bioelectrochemical Reactors

The microbial fuel cell (MFC) provides an inexhaustible electron acceptor to generate current and enhance the degradation of organic compounds. In MFCs with metolachlor as the sole carbon source, the degradation efficiency accelerated by 98%, with 61–76% of enhancement for the degradates, ethane sulfonic acid and oxanilic acid, respectively. According to quantifying primary metabolites of deschloro and metolachlor-2-hydroxyas, dechlorination and alcoholization were deemed as antecedent steps of metolachlor bioelectrochemical degradation. The energy recovery was infeasible by sole addition of metolachlor (at 13 ± 4 °C from equivalent weight of 0.224 mg). In MFCs with metolachlor and sodium acetate as the concomitant carbon sources, the electricity generation recovered to a level comparable to the controls, instead of increasing the removal efficiency of metolachlor. These results suggest that a low-efficiently direct electron transfer occurred between electricigens and metolachlor degraders. The Illumina sequencing showed that species of Paracoccus and Aquamicrobium played a potential degradation effect, while Comamonas sp. replaced Geobacter sp. as the predominant electricigen after addition of metolachlor. This study demonstrates that MFCs could be used as a promising alternative for treatment of chloroacetanilide herbicide contaminated wastewaters by means of a rapidly established active bacterial community. .

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Eicosapentaenoic acid (EPA) induced apoptosis in HepG2 cells through ROS–Ca{sup 2+}–JNK mitochondrial pathways

Highlights: • EPA evoked ROS formation, [Ca{sup 2+}]{sub c} accumulation, the opening of MPTP and the phosphorylation of JNK. • EPA-induced [Ca{sup 2+}]{sub c} elevation was depended on production of ROS. • EPA-induced ROS generation, [Ca{sup 2+}]{sub c} increase, and JNK activated caused MPTP opening. • The apoptosis induced by EPA was related to release of cytochrome C through the MPTP. • EPA induced HepG2 cells apoptosis through ROS–Ca{sup 2+}–JNK mitochondrial pathways. - Abstract: Eicosapentaenoic acid (EPA), a well-known dietary n−3 PUFAS, has been considered to inhibit proliferation of tumor cells. However, the molecular mechanism related to EPA-induced liver cancer cells apoptosis has not been reported. In this study, we investigated the effect of EPA on HepG2 cells proliferation and apoptosis mechanism through mitochondrial pathways. EPA inhibited proliferation of HepG2 cells in a dose-dependent manner and had no significant effect on the cell viability of humor normal liver L-02 cells. It was found that EPA initially evoked ROS formation, leading to [Ca{sup 2+}]{sub c} accumulation and the mitochondrial permeability transition pore (MPTP) opening; EPA-induced HepG2 cells apoptosis was inhibited by N-acetylcysteine (NAC, an inhibitor of ROS), 1,2-bis (2-aminophenoxy) ethane-N,N,N′,N′-tetraacetic acid (BAPTA-AM, a chelator of calcium) and CsA (inhibitor of MPTP). The relationship between ROS production, the increase of cytoplasmic Ca and MPTP opening was detected. It seems that ROS may act as an upstream regulator of EPA-induced [Ca{sup 2+}]{sub c} generation, moreover, generation of ROS, overload of mitochondrial [Ca{sup 2+}]{sub c}, and JNK activated cause the opening of MPTP. Western blotting results showed that EPA elevated the phosphorylation status of JNK, processes associated with the ROS generation. Simultaneously, the apoptosis induced by EPA was related to release of cytochrome C from mitochondria to cytoplasm through the MPTP and activation of caspase-9 and caspase-3. These results suggest that EPA induces apoptosis through ROS–Ca{sup 2+}–JNK mitochondrial pathways.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Enhancement of oxidative dehydrogenation over cerium-doped nickel niobium catalysts and analysis of batch-to-batch variability

Nickel based catalysts are inexpensive and efficient for use in the oxidative dehydrogenation of ethane. NiO doped with niobium and cerium shows increased ethylene production. Small amounts of Ce doped onto a NiNb catalyst led to increased Ni activity. The catalyst that had the highest ethylene production rate per g of catalyst had 1 atom% Ce, 86 at% Ni, and 13 at% Nb (1CeNiNb) while, if surface area is incorporated into the calculation, the catalyst that had the highest ethylene production rate per m 2 was the 0.5CeNiNb catalyst. The ethylene production rates of these Ce-containing catalysts are 27 %-127 % higher than those with NiNb alone previously reported in the literature. Here, to fully understand how cerium affects the NiNb catalyst, the Ce content and effect on active sites has been fully characterized over multiple batches. In doing this, light has been shed on batch-to-batch variability. Characterization techniques such as powder X-ray diffraction, hydrogen temperature programmed reduction, X-ray photoelectron spectroscopy, synchrotron X-ray absorption spectroscopy, and methanol adsorption were used.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Topological evolution and photoluminescent properties of a series of divalent zinc-based metal–organic frameworks tuned via ancillary ligating spacers

The combination of divalent zinc ions, 4-(4-carboxybenzamido)benzoic acid and exo-bidendate bipyridine ligands gave rise to a series of new MOFs: [ZnL(bipy)]·DMF·H{sub 2}O (1), [ZnL(bpe)]·1.5H{sub 2}O (2), [ZnL(bpa)]·4H{sub 2}O (3) and [ZnL(bpp)]·1.75H{sub 2}O (4) (MOF=metal-organic framework, bipy=4,4′-bipyridine, bpe=trans-1,2-bis(4-pyridyl)ethylene, bpa=1,2-bis(4-pyridinyl)ethane, bpp=1,3-bis(4-pyridinyl)propane, H{sub 2}L=4,4′-(carbonylimino)dibenzoic acid). Fine tune over the topology of the MOFs was achieved via systematically varying the geometric length of the second ligating bipyridine ligands. Single-crystal X-ray analysis reveals that complex 1 has a triply interpenetrated three-dimensional (3D) framework with elongated primitive cubic topology, whereas isostructural complexes 2 and 3 each possesses a 6-fold interpenetrated diamondiod 3D framework. Further expansion of the length of the bipyridine ligand to bpp leads to the formation of 4, which features an interesting entangled architecture of 2D→3D parallel polycatenation. In addition, the thermogravimetric analyses and solid-state photoluminescent properties of the selected complexes are investigated. - Graphical abstract: The incorporation of exo-bidendate bipyridine spacers into the Zn–H{sub 2}L system has yielded a series of new MOFs exhibiting topological evolution from 3-fold interpenetration to 6-fold interpenetration and 2D→3D parallel polycatenation. Highlights: ► The effect of the pyridyl-based spacers on the formation of MOFs was explored. ► Fine tune over the topology of the MOFs was achieved. ► An interesting structure of 2D→3D parallel polycatenation is reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Four homochiral coordination polymers contain N-acetyl-L-tyrosine and different N-donor ligand: Influence of metal cations, ancillary ligands and coordination modes

Using the chiral ligand N-acetyl-L-tyrosine (Hacty) and maintaining identical reaction conditions, Zn(II), Co(II), and Cd(II) salts provided four novel homochiral coordination polymers ([Zn(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]·NO{sub 3}·2H{sub 2}O){sub n}1, ([Co(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]·NO{sub 3}·2H{sub 2}O){sub n}2, ([Cd(acty){sub 2}(bipy)H{sub 2}O]·H{sub 2}O){sub n}3, and ([Cd(acty)(bpe){sub 2}(Ac)]·6H{sub 2}O){sub n}4 (bipy=4,4′-bipyridine; bpe=1,2-di(4-pyridyl)ethane) in the presence of ancillary ligands. Compounds 1 and 2 are isostructural 1D chain structures. The neighboring chains are further linked into a 3D supramolecular structure via π⋯π stacking and hydrogen bond interactions. Compound 3 shows a 2D network and 4 generates 1D infinite chains along the c-axis. Compounds 3 and 4 are further connected into 3D supramolecular network by hydrogen bond interactions. More importantly, coordination in acyl oxygen atoms and ancillary ligands (bpe) as monodentate decorating ligands in 4 are rarely reported. Ancillary ligands and metal cations significantly influence the structure of the complexes. The photoluminescence properties of 1, 3, and 4 were studied at room temperature. Circular dichroism (CD) of the complexes have been investigated. - Graphical abstract: Four new homochiral coordination polymers were prepared and structurally characterized, which investigate the influence of the ancillary ligands and metal ions on the design and synthesis of coordination polymers. Display Omitted - Highlights: • It is rarely reported that the chiral coordination polymers prepared with N-acetyl-L-tyrosine ligands. • The alkalescent acetyl oxygen atom is difficult to participate in coordination but it is happened in the N-acetyl-L-tyrosine ligands. • The ancillary ligands (4,4′-bipy and bpe) are present in an unusual coordination modes, monodentate decorating ligands in 1, 2 and 4. • Structure comparative analyses results indicate that the secondary ligands and metal ions influence the fabrication of these inorganic–organic arrangements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Coligand-regulated assembly, fluorescence, and magnetic properties of Co(II) and Cd(II) complexes with a non-coplanar dicarboxylate

A non-coplanar dicarboxylate ndca (H{sub 2}ndca=5-norbornene-2,3-dicarboxylic acid), combining with various dipyridyl-typed tectons, constructs six Cd(II)/Co(II) coordination polymers under hydrothermal conditions, namely [Co(ndca)(H{sub 2}O)]{sub n} (1), ([Co(ndca)(bpe)(H{sub 2}O)]·H{sub 2}O){sub n} (2), [Co(ndca)(bpa){sub 0.5}(H{sub 2}O)]{sub n} (3), [Cd(ndca)(bpe)(H{sub 2}O)]{sub n} (4), ([Cd(ndca)(bpa)(H{sub 2}O)]·0.5H{sub 2}O){sub n} (5), and ([Cd(ndca)(bpp) (H{sub 2}O)]·H{sub 2}O){sub n} (6) (bpe=1,2-di(4-pyridyl)ethylene, bpa=1,2-bi(4-pyridyl)ethane, and bpp=1,3-bis(4-pyridyl)propane). All these compounds contain various metal(II)–carboxylate motifs, including carboxylate binuclear (2, 4, 5), carboxylate chain (1, 6) and carboxylate layer (3), which are further extended by dipyridyl-typed coligands to afford a vast diversity of the structures with 2D pyknotic layers (1, 6), 2D open layer (5), 2D→3D interpenetrated networks (2,4), and 3D pillared-layer framework (3), respectively. In addition, fluorescent spectra of Cd(II) complexes and magnetic properties of Co(II) complexes are also given. - Graphical abstract: Six various cadmium(II)/cobalt(II)–organic frameworks were constructed by 5-norbornene-2,3-dicarboxylic acid and different bis(pyridine) rod-like tectons, and Cd (II) complexes exhibit blue–violet emissions, whereas Co (II) complexes show antiferromagnetic behaviours. Display Omitted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

Four new coordination polymers ([Ni(4-Nbdc)(bpa)(H{sub 2}O)]){sub n} (1), ([Co(4-Nbdc)(bpp) (H{sub 2}O)]){sub n} (2), ([Ni(4-Nbdc)(bpp)(H{sub 2}O)]·H{sub 2}O){sub n} (3), and ([Mn{sub 2}(3-Nbdc){sub 2}(bib){sub 3}]·2H{sub 2}O){sub n} (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal–carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (6{sup 6}) dia topology and (4{sup 4}.6{sup 10}.8)(4{sup 4}.6{sup 2}) fsc topology, and both of them contain metal–carboxylate chains. The carboxyl groups with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)–carboxylate binuclear in 1 (J=1.27 cm{sup −1}) and Ni(II)–carboxylate chain in 3 (J=1.44 cm{sup −1}), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)–carboxylate chain in 4 (J=−0.77 cm{sup −1}). - Highlights: • Four novel coordination polymers were hydrothermally synthesized. • 1 is 1D quasi-trapezoidal chain and 2 is brick-wall layer both with dinuclear units. • 3 and 4 show 3D frameworks both with 1D metal–carboxylate chains. • 1 and 3 exhibit ferromagnetic coupling, while 4 shows antiferromagnetic coupling.

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

Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){sub 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology. • Complex 2 is a 1D “cage+cage”-like chain. • Complex 3 is a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology. • The fluorescent, electrochemical and magnetic properties of 1–3 were reported.

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

Zinc(II) and Cadmium(II) coordination polymers constructed from phenylenediacetate ligands

ABSTRACT: A series of new coordination polymers {[Zn(μ-opda)(μ-bpa)]·2H_2O}{sub n} (1), [Zn(μ{sub 3}-ppda)(μ-bpa)]{sub n} (2), [Cd(μ{sub 3}-ppda)(μ-bpa)]{sub n} (3), [Cd(μ{sub 3}-mpda)(μ-bpa)]{sub n} (4) and [Cd(μ{sub 3}-mpda)(μ-bipy)]{sub n} (5), (o/m/ppda=1,2/1,3/1,4-phenylenediacetate, bpa=1,2-bi(4-pyridyl)ethane, bipy=4,4′-bipyridine) were synthesized. Their structures were characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffraction. Furthermore, the effect of metal sources (zinc acetate and zinc oxide) and acidity of the solution on the structure of the coordination polymers was discussed for complexes 1 and 5, respectively. The single-crystal X-ray crystallographic studies revealed that complexes 1, 3, 4 and 5 are uninodal (4)-connected 2D frameworks and display sql topology with the point symbol of (4{sup 4}.6{sup 2}). Complex 2 is 3D coordination polymer and exhibits pcu topology with the point symbol of (4{sup 12}.6{sup 3}). In addition, the luminescent properties and thermal behavior of all complexes were also investigated. - Graphical abstract: Scheme 1. Topologies of Coordination Polymers Reported in This Paper.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Tuning the microstructures of decavanadate-based supramolecular hybrids via regularly changing the spacers of bis(triazole) ligands

With tuning the ligands from bte, btp, btb to bth, four new decavanadate-based metal–organic hybrid compounds, [Zn(bte)(H{sub 2}O){sub 4}][Zn{sub 2}(bte)(H{sub 2}O){sub 10}](V{sub 10}O{sub 28})·8H{sub 2}O, [Zn{sub 2}(btp){sub 4}(H{sub 2}O){sub 6}](H{sub 2}V{sub 10}O{sub 28})·4H{sub 2}O, [Zn(H{sub 2}O){sub 6}][Zn{sub 2}(btb){sub 2}V{sub 10}O{sub 28}(H{sub 2}O){sub 6}]·4H{sub 2}O, and [Zn{sub 2}(bth)(H{sub 2}O){sub 10}](H{sub 2}V{sub 10}O{sub 28})·6H{sub 2}O (bte=1,2-bis(1,2,4-triazol-1-yl)ethane, btp=1,3-bis(1,2,4-triazol-1-y1)propane, btb=1,4-bis(1,2,4-triazol-1-y1)butane, bth=1,6-bis(1,2,4-triazol-1-y1)hexane), have been synthesized under conventional conditions. The four compounds represent the first examples of decavanadate-based metal–organic hybrids constructed by Zn–bis(triazole) complexes. Their structural analyses show that the four compounds possess different Zn–bis(triazole) structural motifs and various finally structures, which verifies that regular changing the spacers of ligands is an effective strategy to tuning the structures of polyoxometalate-based hybrids. Also, the electrochemical studies show that the compounds have good electrocatalytic activities towards oxidation of nitrite molecules ascribed to V-centers. - Graphical abstract: Four compounds representing the first examples of V{sub 10}O{sub 28}-based hybrids constructed by Zn–bis(triazole) complexes have been synthesized by changing the spacers of the ligands and their electrocatalytic properties have been investigated. - Highlights: • The first examples of V{sub 10}O{sub 28}-based hybrids constructed by Zn-bis(triazole) complexes. • Verifying that changing the spacers of ligands is a strategy to tuning structures. • Showing good electrocatalytic activities toward oxidation of nitrite molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

o-p′-DDT-mediated uterotrophy and gene expression in immature C57BL/6 mice and Sprague–Dawley rats

1,1,1-Trichloro-2,2-bis(2-chlorophenyl-4-chlorophenyl)ethane (o,p′-DDT) is an organochlorine pesticide and endocrine disruptor known to activate the estrogen receptor. Comprehensive ligand- and species-comparative dose- and time-dependent studies were conducted to systematically assess the uterine physiological, morphological and gene expression responses elicited by o,p′-DDT and ethynyl estradiol (EE) in immature ovariectomized C57BL/6 mice and Sprague–Dawley rats. Custom cDNA microarrays were used to identify conserved and divergent differential gene expression responses. A total of 1256 genes were differentially expressed by both ligands in both species, 559 of which exhibited similar temporal expression profiles suggesting that o,p′-DDT elicits estrogenic effects at high doses when compared to EE. However, 51 genes exhibited species-specific uterine expression elicited by o,p′-DDT. For example, carbonic anhydrase 2 exhibited species- and ligand-divergent expression as confirmed by quantitative real-time PCR. The identification of comparable temporal phenotypic responses linked to gene expression demonstrates that systematic comparative gene expression assessments are valuable for elucidating conserved and divergent estrogen signaling mechanisms in rodent uterotrophy. - Highlights: • o,p′-DDT and enthynyl estradiol (EE) both elicit uterotrophy in mice and rats. • o,p′-DDT and EE have different kinetics in uterine wet weight induction. • o,p′-DDT elicited stromal hypertrophy in rats but myometrial hypertrophy in mice. • 1256 genes were differentially expressed by both ligands in both species. • Only 51 genes had species-specific uterine expression.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Using Multiscale Ethane/Methane Observations to Attribute Coal Mine Vent Emissions in the San Juan Basin From 2013 to 2021

Abstract Source attribution of natural gas emissions from fossil fuels in New Mexico's San Juan Basin (SJB) is challenging due to source heterogeneity and emissions transience. We demonstrate that ethane (C 2 H 6 ) to methane (CH 4 ) mixing ratios can identify and separate sources over different scales using various measurement techniques. We report simultaneous CH 4 and C 2 H 6 observations near a coal mine vent and oil and gas (O&G) emission sources using ground‐based in situ measurements in 2020/2021. During these campaigns, we observed a stable coal vent C 2 H 6 :CH 4 ratio of 1.28% ± 0.11%, discernibly different than nearby O&G source ratios ranging from 0.9% to 16.8%. We analyze airborne observations of the SJB taken in 2014/2015 that exhibit similar coal vent ratios and further show the region's heterogeneity. We identify episodic O&G sources, including a gas plant source detected in 2014/2015 that is absent in our 2020/2021 data. We examine total column observations of C 2 H 6 and CH 4 made in 2013 with a solar spectrometer and find a C 2 H 6 :CH 4 ratio of 1.3% ± 0.4% for the coal vent. The stable and unique coal vent ratio relative to other O&G sources in the region is used to demonstrate that consistent attribution is possible using various measurement methods at multiple scales across many years. Finally, we demonstrate that using C 2 H 6 as a proxy for fossil CH 4 inversions can inform detailed basin‐scale inversions, provided we understand source specific changes in the C 2 H 6 :CH 4 ratio like we report in the SJB.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

A high performance lithium–sulfur battery enabled by a fish-scale porous carbon/sulfur composite and symmetric fluorinated diethoxyethane electrolyte

A high performance lithium–sulfur (Li–S) battery comprising a symmetric fluorinated diethoxyethane electrolyte coupled with a fish-scale porous carbon/S composite electrode was demonstrated. 1,2-Bis(1,1,2,2-tetrafluoroethoxy)ethane (TFEE) was first studied as a new electrolyte solvent for Li–S chemistry. When co-mixed with 1,3-dioxolane (DOL), the DOL/TFEE electrolyte suppressed the polysulfide dissolution and shuttling reaction. Lastly, when coupled with a fish-scale porous carbon/S composite electrode, the Li–S cell exhibited a significantly high capacity retention of 99.5% per cycle for 100 cycles, which is far superior to the reported numerous systems.

1,2-bis(1,1,2,2-tetrafluoroethoxy) ethane↗
DOE OSTI2022

Active learning of chemical reaction networks via probabilistic graphical models and Boolean reaction circuits

Discerning networks of many reactions among multiple interconverting species is challenging. Here, we present a reaction network identification methodology. Our methodology enumerates all stoichiometrically and chemically feasible reactions and requires statistical evidence from effluent concentrations for the inclusion or exclusion of each from the reaction network, contrasting with the commonly seen incremental approach and other work of relying heavily upon chemical intuition and assuming the reactions occurring. Using graph theory alongside an active learning design of experiments that propose maximally informative feeds, we identify the underlying reaction network with minimal laboratory runs. Here, we introduce chemistry-probabilistic graphical modeling and Boolean reaction circuits to statistically quantify which reactions occur from effluent concentrations. Our methodology accurately discerns active reactions, as showcased upon a laboratory network of cross-ketonization of furoic and lauric acid and validated upon simulated networks of thermal and CO 2 -assisted ethane dehydrogenation.

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

Simultaneous removal of C 2 H 2 and C 2 H 6 for C 2 H 4 purification by robust MOFs featuring a high density of heteroatoms

Simultaneous removal of C 2 H 6 and C 2 H 2 from C 2 H 4 streams is of great importance in the petrochemical industry but remains a challenging task. To address this challenge, we have selected three isoreticular MOFs with high stability, low cost, and desirable scale-up ability, namely, MOF-303, MIL-160, and CAU-23 and assessed their potential in simultaneous removal of acetylene and ethane for ethylene purification. Each MOF exhibits desirable C 2 H 2 and C 2 H 6 uptake capacity (>5.5 mmol g –1 and >4 mmol g –1 , respectively), as well as good C 2 H 2 /C 2 H 4 selectivity (>2) and C 2 H 6 /C 2 H 4 selectivity (>1.5). Notably, MOF-303 takes up 4.96 mmol g –1 C 2 H 6 at 298 K and 1 bar, the highest value among the three MOFs, with C 2 H 6 /C 2 H 4 selectivity in the range of 1.55–2.47. MIL-160 possesses a very high C 2 H 2 uptake (9.1 mmol g –1 ) and C 2 H 2 /C 2 H 4 selectivity, 10.6 (1 : 1, v/v), at 298 K, much higher than those of all other MOFs tested to date for simultaneous removal of C 2 H 6 and C 2 H 2 from C 2 H 4 . The results from breakthrough experiments confirm that all three MOFs demonstrate excellent performance for C 2 H 4 purification in a ternary mixture of C 2 H 6 /C 2 H 4 /C 2 H 2 (1 : 1 : 1, v/v/v). Here, for MOF-303, MIL-160, and CAU-23, polymer-grade C 2 H 4 up to 0.164, 0.21, and 0.181 mmol g –1 can be obtained from the equimolar ternary mixture in a single separation step from the breakthrough experiment. Additionally, DFT calculations have been performed to further investigate the mechanism of adsorption/separation for C 2 H 6 , C 2 H 4 , and C 2 H 2 .

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

Closure to “Observation-Based Evaluation of Flood Estimation Techniques for a Small Snow-Dominated Basin in the Washington Cascade Mountains”

Here, this paper presents a closure to “Observation-Based Evaluation of Flood Estimation Techniques for a Small Snow-Dominated Basin in the Washington Cascade Mountains” by Hongxiang Yan, Zhuoran Duan, Mark S. Wigmosta, Ning Sun, Ethan D. Gutmann, Bert Kruyt, and Jeffrey R. Arnold. https://doi.org/10.1061/JHYEFF .HEENG-6147.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Investigation of pressure drop in capillary tube for mixed refrigerant Joule-Thomson cryocooler

A capillary tube is commonly used in small capacity refrigeration and air-conditioning systems. It is also a preferred expansion device in mixed refrigerant Joule-Thomson (MR J-T) cryocoolers, since it is inexpensive and simple in configuration. However, the flow inside a capillary tube is complex, since flashing process that occurs in case of refrigeration and air-conditioning systems is metastable. A mixture of refrigerants such as nitrogen, methane, ethane, propane and iso-butane expands below its inversion temperature in the capillary tube of MR J-T cryocooler and reaches cryogenic temperature. The mass flow rate of refrigerant mixture circulating through capillary tube depends on the pressure difference across it. There are many empirical correlations which predict pressure drop across the capillary tube. However, they have not been tested for refrigerant mixtures and for operating conditions of the cryocooler. The present paper assesses the existing empirical correlations for predicting overall pressure drop across the capillary tube for the MR J-T cryocooler. The empirical correlations refer to homogeneous as well as separated flow models. Experiments are carried out to measure the overall pressure drop across the capillary tube for the cooler. Three different compositions of refrigerant mixture are used to study the pressure drop variations. The predicted overall pressure drop across the capillary tube is compared with the experimentally obtained value. The predictions obtained using homogeneous model show better match with the experimental results compared to separated flow models.

42 ENGINEERING↗
DOE OSTI2014

Analytic cubic and quartic force fields using density-functional theory

We present the first analytic implementation of cubic and quartic force constants at the level of Kohn–Sham density-functional theory. The implementation is based on an open-ended formalism for the evaluation of energy derivatives in an atomic-orbital basis. The implementation relies on the availability of open-ended codes for evaluation of one- and two-electron integrals differentiated with respect to nuclear displacements as well as automatic differentiation of the exchange–correlation kernels. We use generalized second-order vibrational perturbation theory to calculate the fundamental frequencies of methane, ethane, benzene, and aniline, comparing B3LYP, BLYP, and Hartree–Fock results. The Hartree–Fock anharmonic corrections agree well with the B3LYP corrections when calculated at the B3LYP geometry and from B3LYP normal coordinates, suggesting that the inclusion of electron correlation is not essential for the reliable calculation of cubic and quartic force constants.

74 ATOMIC AND MOLECULAR PHYSICS↗