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Results for “AROMATICS”

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 1,747 records · Page 97
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Parts per billion detection of uranium with a porphyrinoid-containing nanoparticle and in vivo photoacoustic imaging

Chemical tools that can report radioactive isotopes would be of interest to the defense community. Here in this paper we report –250 nm polymeric nanoparticles containing porphyrinoid macrocycles with and without pre-complexed depleted uranium and demonstrate that the latter species may be detected easily and with high sensitivity via photoacoustic imaging. The porphyrinoid macrocycles used in the present study are non-aromatic in the absence of the uranyl cation, but aromatic after cation complexation. We solubilized both the freebase and metalated forms of the macrocycles in poly(lactic-co-glycolic acid) and found a peak in the photoacoustic spectrum at 910 nm excitation in the case of the uranyl complex. The signal was stable for at least 15 minutes and allowed detection of uranium concentrations down to 6.2 ppb (5.7 nM) in vitro and 0.57 ppm (19 fCi; 0.52 μM) in vivo . Furthermore, to the best of our knowledge, this is the first report of a nanoparticle that detects an actinide cation via photoacoustic imaging.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Magnetic ordering in TCNQ-based metal–organic frameworks with host–guest interactions

Host–guest interactions between the aromatic molecules benzene, toluene, aniline and nitrobenzene and the redox-active TCNQ-based metal–organic framework (MOF), Fe(TCNQ)(4,4'-bpy) (1) (TCNQ = 7,7,8,8-tetracyanoquinodimethane), have been found to modulate spontaneous magnetization behaviours at low temperatures. An analogous MOF, Mn(TCNQ)(4,4'-bpy) (2) with isotropic Mn(II) ions as well as the two-dimensional compound Fe(TCNQ)(DMF)2·2DMF (3·2DMF), were also prepared as models for studying the effects of single-ion magnetic anisotropy and structural distortion on spin canting. In this work, the results indicate guest-dependent long range magnetic ordering occurs at low temperatures, which correlates with the electrostatic and steric effects of the incorporated aromatic guests.

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

Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. Furthermore, these findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

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

Quantitative 13 C NMR characterization of fast pyrolysis oils

Quantitative 13 C NMR analysis of model catalytic fast pyrolysis (CFP) oils following literature procedures showed poor agreement for aromatic hydrocarbons between NMR measured concentrations and actual composition. Furthermore, modifying integration regions based on DEPT analysis for aromatic carbons resulted in better agreement. Solvent effects were also investigated for hydrotreated CFP oil.

09 BIOMASS FUELS↗
DOE OSTI2017

Capping the calix: How toluene completes cesium( i ) coordination with calix[4]pyrrole

The role of solvent in molecular recognition systems is under-researched and often ignored, especially when the solvent is considered “non-interacting”. This study concerns the role of toluene solvent in cesium(I) recognition by calix[4]pyrrole. We show that π-donor interactions bind toluene molecules onto the open face of the cation-receptor complex, thus “capping the calix.” As a result, by characterizing this unusual aromatically-saturated complex, we show how “non-interacting” aromatic solvents can directly coordinate receptor-bound cations and thus influence recognition.

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

Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study

Density functional B3LYP/6-31G(d) and ab initio G3(MP2,CC) calculations have been carried out to determine thermal rate constants of direct H abstraction reactions from four- and five-ring polycyclic aromatic hydrocarbons (PAH) chrysene and benzo[a]pyrene by various radicals abundant in combustion flames, such as H, CH 3 , C 3 H 3 , and OH, using transition state theory. The results show that the H abstraction reactions with OH have the lowest barriers of ~4 kcal mol -1 , followed by those with H and CH 3 with barriers of 16–17 kcal mol -1 , and then with propargyl radicals with barriers of 24–26 kcal mol -1 . Thus, the OH radical is predicted to be the fastest H abstractor from PAH. Even at 2500 K, the rate constant for H abstraction by H is still 34% lower than the rate constant for H abstraction by OH. The reaction with H is calculated to have rate constants 35–19 times higher than those for the reaction with CH 3 due to a more favorable entropic factor. The reactions of H abstraction by C 3 H 3 are predicted to be orders of magnitude slower than the other reactions considered and their equilibrium is strongly shifted toward the reactants, making propargyl an inefficient H abstractor from the aromatics. The calculations showed strong similarity of the reaction energetics in different H abstraction positions of benzo[a]pyrene and chrysene within armchair and zigzag edges in these molecules, but clear distinction between the armchair and zigzag sites. The zigzag sites appear to be more reactive, with H abstraction rate constants by H, CH 3 , and OH being respectively 37–42%, a factor of 2.1, and factors of 8–9 higher than the corresponding rate constants for the H abstraction reactions from armchair sites. Although the barrier heights for the two types of edges are similar, the entropic factor makes zigzag sites more favorable for H abstraction. Rate expressions have been generated for all studied reactions with the goal to rectify current combustion kinetics mechanisms.

Semenikhin, A. S.↗
DOE OSTI2018

H-Abstraction reactions by OH, HO 2 , O, O 2 and benzyl radical addition to O 2 and their implications for kinetic modelling of toluene oxidation

Here, alkylated aromatics constitute a significant fraction of the components commonly found in commercial fuels. Toluene is typically considered as a reference fuel. Together with n-heptane and iso-octane, it allows for realistic emulations of the behavior of real fuels by the means of surrogate mixture formulations. Moreover, it is a key precursor for the formation of poly-aromatic hydrocarbons, which are of relevance to understanding soot growth and oxidation mechanisms. In this study the POLIMI kinetic model is first updated based on the literature and on recent kinetic modelling studies of toluene pyrolysis and oxidation. Then, important reaction pathways are investigated by means of high-level theoretical methods, thereby advancing the present knowledge on toluene oxidation. H-Abstraction reactions by OH, HO 2 , O and O 2 , and the reactivity on the multi well benzyl-oxygen (C 6 H 5 CH 2 + O 2 ) potential energy surface (PES) were investigated using electronic structure calculations, transition state theory in its conventional, variational, and variable reaction coordinate forms (VRC-TST), and master equation calculations. Exploration of the effect on POLIMI model performance of literature rate constants and of the present calculations provides valuable guidelines for implementation of the new rate parameters in existing toluene kinetic models.

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

Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration

Catalytic fast pyrolysis (CFP) has emerged as an attractive process for the conversion of lignocellulosic biomass into renewable fuels and products. Considerable research and development has focused on using circulating-bed reactors with zeolite catalysts (e.g., HZSM-5) for CFP because of their propensity to form gasoline-range aromatic hydrocarbons. However, the high selectivity for aromatics comes at the expense of low carbon yield, a key economic driver for this process. In this contribution, we evaluate non-zeolite catalysts in a fixed-bed reactor configuration for an integrated CFP process to produce fuel blendstocks from lignocellulosic biomass. These experimental efforts are coupled with technoeconomic analysis (TEA) to benchmark the process and guide research and development activities to minimize costs. The results indicate that CFP bio-oil can be produced from pine with improved yield by using a bifunctional metal-acid 2 wt% Pt/TiO 2 catalyst in a fixed-bed reactor operated with co-fed H 2 at near atmospheric pressure, as compared to H-ZSM5 in a circulating-bed reactor. The Pt/TiO 2 catalyst exhibited good stability over 13 reaction-regeneration cycles with no evidence of irreversible deactivation. The CFP bio-oil was continuously hydrotreated for 140 h time-on-stream using a single-stage system with 84 wt% of the hydrotreated product having a boiling point in the gasoline and distillate range. This integrated biomass-to-blendstock process was determined to exhibit an energy efficiency of 50% and a carbon efficiency of 38%, based on the experimental results and process modelling. TEA of the integrated process revealed a modelled minimum fuel selling price (MFSP) of $4.34 per gasoline gallon equivalent (GGE), which represents a cost reduction of $0.85 GGE -1 compared to values reported for CFP with a zeolite catalyst. TEA also indicated that catalyst cost was a significant factor influencing the MFSP, which informed additional CFP experiments in which lower-cost Mo2C and high-dispersion 0.5 wt% Pt/TiO 2 catalysts were synthesized and evaluated. These materials demonstrated CFP carbon yield and oil oxygen content similar to those of the 2 wt% Pt/TiO 2 catalyst, offering proof-of-concept that the lower-cost catalysts can be effective for CFP and providing a route to reduce the modelled MFSP to $3.86–3.91 GGE -1 . This report links foundational science and applied engineering to demonstrate the potential of fixed-bed CFP and highlights the impact of coupled TEA to guide research activities towards cost reductions.

09 BIOMASS FUELS↗
DOE OSTI2018

Revisiting alkaline aerobic lignin oxidation

Lignin conversion to renewable chemicals is a promising means to improve the economic viability of lignocellulosic biorefineries. Alkaline aerobic oxidation of lignin has long been employed for production of aromatic compounds such as vanillin and syringaldehyde, but this approach primarily focuses on condensed substrates such as Kraft lignin and lignosulfonates. Conversely, emerging lignocellulosic biorefinery schemes enable the production of more native-like, reactive lignin. Here, we revisit alkaline aerobic oxidation of highly reactive lignin substrates to understand the impact of reaction conditions and catalyst choice on product yield and distribution. The oxidation of native poplar lignin was studied as a function of temperature, NaOH loading, reaction time, and oxygen partial pressure. Besides vanillin and syringaldehyde, other oxidation products include acetosyringone and vanillic, syringic, and p-hydroxybenzoic acids. Reactions with vanillin and syringaldehyde indicated that these compounds are further oxidized to non-aromatic carboxylic acids during alkaline aerobic oxidation, with syringaldehyde being substantially more reactive than vanillin. The production of phenolic compounds from lignin is favored by high NaOH loadings and temperatures, but short reaction times, as the products degrade rapidly, which is further exacerbated by the presence of oxygen. Under optimal conditions, a phenolic monomer yield of 30 wt% was obtained from poplar lignin. Testing a range of catalysts showed that Cu-containing catalysts, such as CuSO 4 and LaMn 0.8 Cu 0.2 O 3 , accelerate product formation; specifically, the catalyst does not increase the maximum yield, but expands the operating window in which high product yields are obtainable. We also demonstrate that other native and isolated lignin substrates that are significantly chemically modified are effectively converted to phenolic compounds. Finally, alkaline aerobic oxidation of native lignins was compared to nitrobenzene oxidation and reductive catalytic fractionation, as these methods constitute suitable benchmarks for lignin depolymerization. While nitrobenzene oxidation achieved a somewhat higher yield, similar monomer yields were obtained through RCF and alkaline aerobic oxidation, especially for lignins with a high guaiacyl- and/or p-hydroxyphenyl-content, as syringyl units are more unstable during oxidation. Overall, this study highlights the potential for aerobic lignin oxidation revisited on native-like lignin substrates.

09 BIOMASS FUELS↗
DOE OSTI2019

Post-synthetic modulation of the charge distribution in a metal–organic framework for optimal binding of carbon dioxide and sulfur dioxide

Modulation of pore environment is an effective strategy to optimize guest binding in porous materials. We report the post-synthetic modification of the charge distribution in a charged metal–organic framework, MFM-305-CH3, [Al(OH)(L)]Cl, [(H2L)Cl ¼ 3,5-dicarboxy-1-methylpyridinium chloride] and its effect on guest binding. MFM-305-CH3 shows a distribution of cationic (methylpyridinium) and anionic (chloride) centers and can be modified to release free pyridyl N-centres by thermal demethylation of the 1- methylpyridinium moiety to give the neutral isostructural MFM-305. This leads simultaneously to enhanced adsorption capacities and selectivities (two parameters that often change in opposite directions) for CO2 and SO2 in MFM-305. The host–guest binding has been comprehensively investigated by in situ synchrotron X-ray and neutron powder diffraction, inelastic neutron scattering, synchrotron infrared and 2 H NMR spectroscopy and theoretical modelling to reveal the binding domains of CO2 and SO2 in these materials. CO2 and SO2 binding in MFM-305-CH3 is shown to occur via hydrogen bonding to the methyl and aromatic-CH groups, with a long range interaction to chloride for CO2. In MFM-305 the hydroxyl, pyridyl and aromatic C–H groups bind CO2 and SO2 more effectively via hydrogen bonds and dipole interactions. Post-synthetic modification via dealkylation of the as-synthesised metal–organic framework is a powerful route to the synthesis of materials incorporating active polar groups that cannot be prepared directly.

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

Investigation of solvent effects on the hydrodeoxygenation of guaiacol over Ru catalysts

The effects of a liquid phase environment on the hydrodeoxygenation of guaiacol, a prototypical lignin derived compound, have been investigated over a Ru catalyst from first principles. A microkinetic reactor model with parameters obtained from density functional theory and implicit solvation schemes was developed to study the effects of condensed phases on the reaction mechanism and kinetic parameters. Phenol was found to be the major aromatic product across all reaction environments. Our model predicts that less protic solvents such as 1-butanol, diethyl ether, and n-hexane have a positive effect on the reaction kinetics for the production of phenolics relative to vapor and aqueous reaction environments. The dominant reaction mechanism for aromatics production remains unchanged across all reaction media. Next, we investigated the possibility of cycloalkane production through hydrogenation of phenol in vapor and liquid phase environments. Our calculations indicated that the reaction pathway for cycloalkane production from phenol will most likely follow an initial dehydrogenation of the hydroxyl group. Based on the vapor phase density functional theory calculations, we proposed a probable reaction pathway and calculated the condensed phase effects along this reaction route. We observed that an aqueous phase has a more favorable effect for cycloalkane production from phenol relative to vapor phase and other less protic solvent environments.

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

Electrocatalytic cleavage of lignin model dimers using ruthenium supported on activated carbon cloth

Biomass lignin is the largest natural source of renewable aromatic compounds, creating an opportunity for its use as a feedstock provided that deconstruction and upgrading methods become available. Valorization of lignin is challenging because its complex structure is naturally recalcitrant to biological degradation. Deconstruction of this amorphous cross-linked polymer requires cleavage of aryl ether bonds, which account for more than half of the linkages between lignin's phenylpropanoid building blocks. High temperature cracking of lignin is possible via pyrolysis, but linkages such as 4-O-5 bonds are resistant to thermal degradation. Electrocatalytic hydrogenation offers a mild alternative; operated at low temperature and atmospheric pressure, it cleaves ether bonds while saturating aromatic rings with in situ generated hydrogen. To investigate the use of catalytic ruthenium supported on activated carbon cloth to cleave 4-O-5 bonds, model compounds that exhibit this linkage were selected, including 3-phenoxyphenol, 4-phenoxyphenol, 3-phenoxyanisole, and 3-phenoxytoluene. The two phenols, 3-phenoxyphenol and 4-phenoxyphenol, were cleaved and hydrogenated to form cyclohexanol. 3-Phenoxyanisole and 3-phenoxytoluene were also cleaved but with lower conversion rates and cyclohexanol yields. Alkaline electrolyte solutions showed the highest cyclohexanol yields for both substrates. Increasing substrate concentrations from 10 mM to 40 mM increased faradaic efficiency to 25%, while decreasing current density from 100 mA (33.33 mA cm -2 ) to 20 mA (6.67 mA cm -2 ) greatly improved the faradaic efficiency to 96%.

09 BIOMASS FUELS↗
DOE OSTI2020

Diazo coupling for surface attachment of small molecules to TiO 2 nanoparticles

Robust surface attachment of molecular species to metal oxide semiconductors is desirable for many applications. In this work, we report the interfacial diazo coupling of surface-bound amines with aromatics to bind them to the surface of TiO 2 nanoparticles via a robust siloxane anchor and a diazo link. The technique shows potential for the inexpensive, stable, modular and tunable attachment of molecules to metal oxide surfaces.

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

On the mechanism of soot nucleation

The mechanism of carbon particulate (soot) inception has been a subject of numerous studies and debates. The article begins with a critical review of prior proposals, proceeds to the analysis of factors enabling the development of a meaningful nucleation flux, and then introduces new ideas that lead to the fulfillment of these requirements. In the new proposal, a rotationally-activated dimer is formed in the collision of an aromatic molecule and an aromatic radical; the two react during the lifetime of the dimer to form a stable, doubly-bonded bridge between them, with the reaction rooted in a five-member ring present on the molecule edge. Several such reactions were examined theoretically and the most promising one generated a measurable nucleation flux. The consistency of the proposed model with known aspects of soot particle nanostructure is discussed. Here, the foundation of the new model is fundamentally the H-Abstraction-Carbon-Addition (HACA) mechanism with the reaction affinity enhanced by rotational excitation.

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

On the mechanism of soot nucleation. II. E-bridge formation at the PAH bay

A recently proposed mechanism of soot nucleation based upon the formation of a rotationally-activated dimer in the collision of an aromatic molecule and a radical leading to a stable, doubly-bonded E-bridge between them, rooted in the existence of a five-membered ring on the molecule edge, has been further investigated with a focus on the 5-6 E-bridge forming in the reaction of a PAH cyclopenta group with a bay site of another PAH. As a prototype reaction of this kind, we examined the reaction between 4-phenanthrenyl and acenaphthylene and, to project these results to larger aromatic structures, we also explored the size effect of the E-bridge forming reactions by computing the 1-naphthyl + acenaphthylene system and comparing these results with the prior results for pyrenyl + acepyrene. The two systems have been studied through high-level G3(MP2,CC)//B3LYP/6-311G(d,p) ab initio calculations of their potential energy surfaces combined with the RRKM/Master Equation calculations of reaction rate constants. With PAH monomers of similar sizes involved, the formation of E-bridge structures at the bay radical sites appeared to be faster and lead to increased nucleation rates as compared to the zigzag-forming ones. Furthermore, a model combining both the bay and zigzag rotationally-induced formation of E-bridges successfully reaches the level of nucleation fluxes comparable to those of the irreversible pyrene dimerization, thus affirming the rotationally-activated dimerization as a feasible mechanism for soot particle nucleation.

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

Gas phase formation of cyclopentanaphthalene (benzindene) isomers via reactions of 5- and 6-indenyl radicals with vinylacetylene

The tricyclic polycyclic aromatic hydrocarbons (PAHs) 3H-cyclopenta[a]naphthalene (C 13 H 10 ), 1H-cyclopenta[b]naphthalene (C 13 H 10 ) and 1H-cyclopenta[a]naphthalene (C 13 H 10 ) along with their indene-based bicyclic isomers (E)-5-(but-1-en-3-yn-1-yl)-1H-indene, (E)-6-(but-1-en-3-yn-1-yl)-1H-indene, 5-(but-3-ene-1-yn-1-yl)-1H-in-dene, and 6-(but-3-ene-1-yn-1-yl)-1H-indene were formed via a “directed synthesis” in a high-temperature chemical micro reactor at the temperature of 1300 ± 10 K through the reactions of the 5- and 6-indenyl radicals (C 9 H 7 ˙) with vinylacetylene (C 4 H 4 ). The isomer distributions were probed utilizing tunable vacuum ultraviolet light by recording the photoionization efficiency curves at mass-to-charge of m/z = 166 (C 13 H 10 ) and 167 ( 13 CC 12 H 10 ) of the products in a supersonic molecular beam. Here, the underlying reaction mechanisms involve the initial formation of van-der-Waals complexes followed by addition of the 5- and 6-indenyl radicals to vinylacetylene via submerged barriers, followed by isomerization (hydrogen shifts, ring closures), and termination via atomic hydrogen elimination accompanied by aromatization. All the barriers involved in the formation of 3H-cyclopenta[a]naphthalene, 1H-cyclopenta[b]naphthalene and 1H-cyclopenta[a]naphthalene are submerged with respect to the reactants indicating that the mechanisms are in fact barrierless, potentially forming PAHs via the hydrogen abstraction – vinylacetylene addition (HAVA) pathway in the cold molecular clouds such as Taurus Molecular Cloud-1 (TMC-1) at temperatures as low as 10 K.

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

Thermodynamic consequences of Tyr to Trp mutations in the cation–π-mediated binding of trimethyllysine by the HP1 chromodomain

Evolution has converged on cation–p interactions for recognition of quaternary alkyl ammonium groups such as trimethyllysine (Kme3). While computational modelling indicates that Trp provides the strongest cation–p interaction of the native aromatic amino acids, there is limited corroborative data from measurements within proteins. Herein we investigate a Tyr to Trp mutation in the binding pocket of the HP1 chromodomain, a reader protein that recognizes Kme3. Binding studies demonstrate that the Trpmediated cation–p interaction is about -5 kcal mol -1 stronger, and the Y24W crystal structure shows that the mutation is not perturbing. Quantum mechanical calculations indicate that greater enthalpic binding is predominantly due to increased cation–π interactions. NMR studies indicate that differences in the unbound state of the Y24W mutation lead to enthalpy–entropy compensation. These results provide direct experimental quantification of Trp versus Tyr in a cation–π interaction and afford insight into the conservation of aromatic cage residues in Kme3 reader domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗