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At least 505 records · Page 28

A new hydrous iron oxide phase stable at mid-mantle pressures

The amount of hydrogen stored in the Earth's interior is important for a range of issues, including the volatile incorporation during the Earth formation and the co-evolution of the atmosphere, the hydrosphere, and the interior. Recent experiments found titanium bearing ε-FeOOH in a hydrous basaltic system at 12–19 GPa and 1300 K. Pyrite-type FeOOH was found to be stable at pressures higher than 80 GPa. These discoveries suggest possible hydrogen storage in the mantle transition zone and in the mantle below 1800 km depths, respectively. However, it remains uncertain how the potential deep hydrogen storage can be connected to the shallower storage. Here, we report a new hydrous iron oxide (η-Fe 12 O 18+x / 2 H x , x ≈ 2) stable at pressures between the stability fields of the ε- and the pyrite-type FeOOH. Our experiment also shows that the new η phase can exist together with the major lower mantle minerals including bridgmanite and periclase, making it an important hydrogen-bearing phase in the Earth's deep interior. Because of its limited H 2 O storage capacity, which is less than 1/6 of the storage capacity of the pyrite-type phase and the ε phase, the stability of the η phase would result in H 2 O loss during water transport in the mid mantle and therefore limit the amount of H 2 O potentially stored in the Fe–O–H system of the lower mantle. As a result, the large channel in the crystal structure of the η phase could provide potential storage sites for other volatile elements in the deep mantle.

58 GEOSCIENCES↗

Effect of pretreatment conditions on Fe-ZSM-5 properties and performance for Fischer–Tropsch synthesis

Iron supported on ZSM-5 is a widely studied catalyst for Fischer–Tropsch synthesis (FTS). Iron is activated with H 2 , CO, or a mixture of CO and H 2 prior to FTS, resulting in phase transformations that make it challenging to understand structure–property relationships. Furthermore, in this work, we demonstrate that increasing the pretreatment temperature of Fe–Na-ZSM-5 reduces CO conversion irrespective of the reductant, but the product selectivity, iron particle size, composition, CO adsorption properties, and zeolite structure is dependent on both the pretreatment temperature and reductant. Pretreatment of Fe–Na-ZSM-5 in H 2 induces sintering of iron particles, increasing C 2 –C 4 olefins and C 5+ hydrocarbons selectivity from 19.0% and 14.0% at 350 °C to 28.2% and 25.4% at 770 °C, respectively. Conversely, CO pretreatment facilitates carbide formation, coke deposition, and CH 4 formation.

36 MATERIALS SCIENCE↗

Understanding CO 2 adsorption on the surfaces of SrO and its hydroxylated variants Sr(OH) 2 · n H 2 O ( n = 0, 1, 8)

Strontium oxide (SrO) is a promising material for CO 2 capture through a reversible cycle of carbonation and calcination, where SrO reacts with CO 2 to form SrCO 3 and can be regenerated by calcination. In the presence of moisture, SrO forms strontium hydroxide and its hydrates (Sr(OH) 2 ·nH 2 O). Here, this study, which employs density functional theory, investigates the CO 2 adsorption mechanism of these processes on various crystal surfaces, including SrO, Sr(OH) 2 , Sr(OH) 2 ·1H 2 O, and Sr(OH) 2 ·8H 2 O. A significant finding is that the interaction of CO 2 with these surfaces leads to carbonate/bicarbonate formation via electron transfer, with notable differences in CO 2 orientation and bond characteristics between SrO surfaces and its hydroxylated surfaces. To explore the effects of moisture on CO 2 adsorption, H 2 O adsorption on these stable surfaces was investigated. The results showed that H 2 O reacts with the SrO (100) surface to form hydroxyl (OH) groups while it bonds with the surfaces of Sr(OH) 2 ·nH 2 O (n = 0, 1, 8) with hydrogen bonding. A small amount of H 2 O can enhance CO2 adsorption while a large amount of H 2 O could decrease the capability of CO 2 adsorption.

CO2 capture↗

Machine learning assisted search for Fe–Co–C ternary compounds with high magnetic anisotropy

We employ a machine learning (ML)-guided framework to explore rare earth free magnetic materials, specifically focusing on Fe–Co–C ternary compounds for potential use in permanent magnets. Utilizing a specifically trained crystal graph convolutional neural network model, we efficiently screen a vast space of nearly a million substitutional structures to select 620 promising structures for further investigation by first-principles calculation. We predict five low-energy metastable Fe–Co–C compounds with formation energy less than 150 meV/atom above the convex hull. These compounds exhibit high magnetization (Js > 1.0 T) and significant magnetic anisotropy (K1 > 1.0 MJ/m3), making them promising candidates for permanent magnet applications. The phonon calculations indicate these compounds are dynamically stable. Our ML-guided framework demonstrates the utility of rapidly identifying novel materials with tailored magnetic properties.

36 MATERIALS SCIENCE↗

Low-dimensional metal–organic frameworks: a pathway to design, explore and tune magnetic structures

Here, the magnetic structure adopted by a material relies on symmetry, the hierarchy of exchange interactions between magnetic ions and local anisotropy. A direct pathway to control the magnetic interactions is to enforce dimensionality within the material, from zero-dimensional isolated magnetic ions, one-dimensional (1D) spin-chains, two-dimensional (2D) layers to three-dimensional (3D) order. Being able to design a material with a specific dimensionality for the phenomena of interest is non-trivial. While many advances have been made in the area of inorganic magnetic materials, organic compounds offer distinct and potentially more fertile ground for material design. In particular magnetic metal–organic frameworks (mMOFs) combine magnetism with non-magnetic property functionality on the organic linkers within the structural framework, which can further be tuned with mild perturbations of pressure and field to induce phase transitions. Here, it is examined how neutron scattering measurements on mMOFs can be used to directly determine the magnetic structure when the magnetic ions are in a 2D layered environment within the wider 3D crystalline framework. The hydrated formate, in deuterated form, Co(DCOO) 2 ·2D 2 O, which was one of the first magnetic MOFs to be investigated with neutron diffraction, is reinvestigated as an exemplar case.

magnetism↗

Hydrazinoacetic acid is a biosynthetic precursor of the bacterially produced nitramine, N -nitroglycine

Nitramines [R(R′)N–NO 2 ; R,R′=H or alkyl] are valuable synthetic products, but knowledge of the biosynthetic processes that generate these compounds is limited. This work sought to elucidate the biosynthesis of a nitramine natural product, N-nitroglycine (NNG) by Streptomyces noursei . Stable isotope studies showed that S. noursei cells supplemented with L-(ε- 15 N)lysine, ( 15 N)glycine, or ( 13 C)hydrazinoacetic acid (HAA) incorporated 67%, 88%, and 67% of the isotope label into NNG, respectively, indicating that these compounds are biosynthetic precursors of NNG. Liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) of 15 N-Lys-labeled NNG confirmed that the nitro nitrogen of NNG originates from Lys. Bioinformatics analysis of the S. noursei genome showed evidence for a biosynthetic gene cluster (BGC) that contained machinery for HAA biosynthesis ( nngKLM ), consistent with the results of the isotope labeling. In vitro reconstitution of the gene products produced HAA. The borders of this BGC were defined by cross-referencing the predicted BGC with previously published differential proteomics data. Furthermore, we show that azaserine is produced alongside NNG in S. noursei cultures, linking the two biosynthetic pathways via a proposed nitrosamine biosynthetic intermediate. Finally, the oxygen balance for NNG is −20.2% for the formation of carbon dioxide (CO 2 ), which is comparable to that of hexahydro-1,3,5- trinitro-1,3,5-triazene (common name: RDX; −21.6%). Crystal structure data of NNG indicate that the unit crystalizes as a pure material, not a hydrate, suggesting a favorable energetic crystallization phase. The combined results suggest a route that, with further development, could lead to sustainable production of energetic nitramines via synthetic biology or biocatalytic approaches.

biosynthesis↗

Grid-Scale, Long-Term Energy Storage: Repurposing Hydrocarbon Reservoirs, Resources, and Infrastructure to Store CO 2 and Heat (Mid-Project Progress Report)

The purpose of this project is to create a viable business case for CO 2 capture, use, and storage (CCUS) by enabling grid-scale, long-term energy storage in mature hydrocarbon reservoirs and saline aquifers. Our CCUS approach, called the Earth Battery, is based on patents issued to Lawrence Livermore National Laboratory on Multi-Fluid Geo-Energy and Earth Battery Systems and to the University of Minnesota and TerraCOH, Inc. on CO 2 Plume Geothermal (CPG). Excess energy can be used to compress and store CO 2 and hot brine underground in permeable formations, including: (1) saline aquifers suitable for geologic CO 2 storage (GCS) and (2) hydrocarbon reservoirs, the focus of this project featuring a pilot test in a mature oil and natural gas (NG) field. Excess energy can come in the form of excess electricity from the grid or excess NG that does not have a market. It can also come in the form of excess heat from other sources, such as from the heat of air or CO 2 compression or from a nearby base-load power plant or solar thermal energy (STE) facility, when heat is not needed to generate electricity from those sources.

15 GEOTHERMAL ENERGY↗

Energetics of the protonation of CO - Implications for the observation of HOC(+) in dense interstellar clouds

A number of molecular species on the H3CO(+) energy hypersurface is examined. Ab initio molecular orbital theory is used to determine the structures and relative energetics of the two isomers of HCO(+) and HOC(+) together with the affinity of CO for protonation at either end. The proton affinities of H2 and H2CO are also examined. The calculations are performed using large basis sets and include the effects of electron correlation. The calculated vibrational frequencies are used to correct for zero point energy differences. The results show that the proton affinities of H2 and CO to form HOC(+) are within 1 kcal of each other. The calculations demonstrate that there is no thermodynamic driving force to form HOC(+) in collisions of H3(+) with CO, and that the formation of HCO(+) in such collisions is very exoergic. A plausible mechanism is suggested to explain the differences observed between the laboratory and the interstellar medium.

Dixon, D.↗

The interiors of Pluto and Charon - Structure, composition, and implications

Recent models of the internal structure of Pluto and Charon, made possible by analysis of the Pluto/Charon mutual events are reviewed. At a mean density of just over 2 g/cu cm and a predicted rock mass fraction of roughly 0.7, the Pluto/Charon system is significantly rockier than the icy satellites of the giant planets, a contrast which may reflect its formation in a CO-rich outer solar nebula rather than a circumplanetary nebula. Pluto and Charon may in fact be so rocky that they lost volatiles early in their history (possibly during a Charon-forming impact event), although this is still an open issue.

Simonelli, Damon P.↗

Is a local bar a good place to find a companion? The near infrared morphology of Maffei 2

Maffei 2 is one of the closest large spiral galaxies lying just beyond the Local Group. It would probably be one of the most heavily studied galaxies in the sky were it not for the approximately 5 magnitudes of visual extinction resulting from its position behind the Galactic plane. It is the site of a burst of nuclear star formation indicated by strong infrared and radii continuum emission. Interferometric maps of CO-12 and CO-13 emission indicate that star formation is associated with a barlike structure consisting of arms of molecular gas that extend from within approximately 50 pc of the dynamical center out to a radius of at least 500 pc. HI maps have shown the galaxy to have an angular extent of approximately 15 feet and a neutral gas mass typical of a large spiral galaxy.

Hurt, Robert L.↗

Effects of Structure and Hydrodynamics on the Sooting Behavior of Spherical Microgravity Diffusion Flames

Recent experimental, numerical and analytical work has shown that the stoichiometric mixture fraction (Z(sub st)) can have a profound effect on soot formation in diffusion flames. These findings were obtained at constant flame temperature (T(sub ad)), employing the approach described in Du and Axelbaum (1995, 1996). For example, a fuel mixture containing 1 mole of ethylene and 11.28 moles of nitrogen burning in pure oxygen ((Z(sub st)) = 0.78) has the same adiabatic flame temperature (2370 K) as that of pure ethylene burning in air ((Z(sub st)) = 0.064). An important finding of these works was that at sufficiently high (Z(sub st)), flames remain blue as strain rate approaches zero in counterflow flames, or as flame height and residence time approach infinity in coflowing flames. Lin and Faeth (1996a) coined the term permanently blue to describe such flames. Two theories have been proposed to explain the appearance of permanently-blue flames at high (Z(sub st)). They are based on (1) hydrodynamics and (2) flame structure. Previous experimental studies in normal gravity are not definitive as to which, if either, mechanism is dominant because both hydrodynamics and structure suppress soot formation at high (Z(sub st)) in coflowing and counterflowing diffusion flames. In counterflow flames with (Z(sub st)) < 0.5 streamlines at the flame sheet are directed toward the fuel. Newly formed soot is convected into richer regions, favoring soot growth over oxidation. For (Z(sub st)) > 0.5, convection at the flame is toward the oxidizer, thus enhancing soot oxidization. Thus, in counterflow flames, hydrodynamics causes soot to be convected towards the oxidizer at high (Z(sub st)) which suppresses soot formation. Axelbaum and co-workers maintain that while the direction of convection can impact soot growth and oxidation, these processes alone cannot cause permanently-blue flames. Soot growth and oxidation are dependent on the existence of soot particles and the presence of soot is invariably accompanied by yellow luminosity. Soot-particle inception, on the other hand, arises from gas-phase reactions and its dependence on flow direction is weak, similar to that of other gas-phase reactions in flames. For example, when the flame moves across the stagnation plane no significant changes in flame chemistry are observed. Furthermore, since the soot-inception zone has a finite thickness, soot has been produced in counterflow flames with (Z(sub st)) > 0.5. For large (Z(sub st)) the fuel concentration decreases and oxygen concentration increases in the soot forming regions of the flame. This yields a shift in the OH profile toward the fuel side of the flame, and this shift can dramatically influence soot inception because it essentially narrows the soot inception zone. Soot-free (permanently-blue) conditions can be realized when the structure of the flame is adjusted to the extent that significant oxidizing species exist on the fuel side of the flame at temperatures above the critical temperature for soot inception, ca. 1250 K. In previously considered flames it was impossible to independently vary flame structure and convection direction. In contrast, spherical diffusion flames (which generally require microgravity) allow both properties to be varied independently. We altered structure (Z(sub st)) by exchanging inert between the oxidizer and the fuel and we independently varied convection direction at the flame sheet by interchanging the injected and ambient gases. In this work we established four flames: (a) ethylene issuing into air, (b) diluted ethylene issuing into oxygen, (c) air issuing into ethylene, and (d) oxygen issuing into diluted ethylene. (Z(sub st)) is 0.064 in flames (a) and (c) and 0.78 in flames (b) and (d). The convection direction is from fuel to oxidizer in flames (a) and (b) and from oxidizer to fuel in flames (c) and (d). Under the assumption of equal diffusivities of all species and heat, the stoichiometric contours of these flames have identical temperatures and nitrogen concentrations.

Sunderland, P. B.↗

Frostwing Co-Operation in Aircraft Icing Research

e aerodynamic effects of Cold Soaked Fuel Frost have become increasingly significant as airworthiness authorities have been asked to allow it during aircraft take-off. The Federal Aviation Administration and the Finnish Transport Safety Agency signed a Research Agreement in aircraft icing research in 2015 and started a research co-operation in frost formation studies, computational fluid dynamics for ground de/anti-icing fluids, and de/anti-icing fluids aerodynamic characteristics. The main effort has been so far on the formation and aerodynamic effects of CSFF. To investigate the effects, a generic high-lift common research wind tunnel model and DLR-F15 airfoil, representing the wing of a modern jet aircraft, was built including a wing tank cooling system. Real frost was generated on the wing in a wind tunnel test section and the frost thickness was measured with an Elcometer gauge. Frost surface geometry was measured with laser scanning and photogrammetry. The aerodynamic effect of the frost was studied in a simulated aircraft take-off sequence, in which the speed was accelerated to a typical rotation speed and the wing model was then rotated to an angle of attack used at initial climb. Time histories of the lift coefficient were measured with a force balance. The experiments showed that depending on the ambient temperature the frost may evaporate/melt during the take-off sequence. Lift losses after rotation with CSFF contamination at ambient temperatures of 4˚ to 7˚C above freezing point were measured to be 4 to 5 % for roughness values, k/c, below 10(exp -3). For comparison, lift loss tests with typical anti-icing fluids were to roughly equal lift losses. This paper gives an overview of the performed activities.

Koivisto, Pekka↗

Improved Rainfall Data in the Philippines through Concurrent Use of GPM IMERG and Ground-Based Measurements

The availability of accurate and reliable rainfall data that are applicable to various phenomenological, climatological, and modeling studies is important, especially in the Philippines, which is considered to be highly vulnerable to natural hazards and a changing climate. The presented strategy involved constructing a dataset consisting of synoptic data, automatic rain gauge (ARG) measurements, and satellite data that are co-registered, consistent, and formatted in the same manner. Although sparse in number, the synoptic stations provide the most accurate rainfall information and were used as the baseline for creating the dataset. The ARGs that are within a distance of 1 km to the synoptic stations were used to determine the correction factors needed to make the synoptic and ARG data consistent. Subsequently, the corrected ARGs were used to make the satellite IMERG data consistent with both ARG and synoptic data. In case of the latter, only IMERG pixels with at least 10 ARGs within the relatively large footprint of the satellite sensor were used in estimating the required correction parameters derived from a combination of a power transform and linear regression correction techniques. The final results show good agreement of synoptic and corrected ARG data with correlation coefficients of 0.94 and 0.97 for the 10 day and monthly data, respectively, and improvement in the linear regression slope from 0.67 to 0.90 for 10 day data, and 0.70 to 0.94 for monthly data. In addition, the corrected ARG data agree well with the corrected IMERG data, with correlation coefficients of 0.88 and 0.93 for the 10 day and monthly data, respectively, and an improvement in slope from 0.66 to 0.87 for 10 day data, and 0.74 to 0.99 for monthly data. The merit of using a combined dataset is illustrated through comparative analyses of the IMERG data and spatially interpolated synoptic and ARG data. The results show general agreements in spatial patterns of rainfall across the datasets, especially in areas where in situ measurements are recorded. The observed discrepancy when ground data is limited emphasizes the need for satellite IMERG data to obtain the true spatial patterns of rainfall distribution.

rainfall↗

BETO 2021 Peer Review - Cell Free and Immobilization Technologies (CFIT)

Today, several key factors negatively impact the production of fuels and chemicals from renewable sources. Common hindrances in the biological production of biochemicals are: (1) end-product or intermediate toxicity to the microbial biocatalyst, (2) the diversion of carbon to biomass formation, and (3) co-production of undesired byproducts. A particularly attractive alternative is to eliminate the biocatalyst entirely and instead operate the desired metabolic pathways in isolation, thus circumventing the roadblocks of biological toxicity, lower yields, and lack of specificity. However, cell-free enzyme systems still suffer from low productivities owing in part to the effects of free diffusion of intermediates, lack of long term enzyme stability, cofactor cost or inefficient recycling rates, and finally, the cost of enzyme production/purification. This project represents a new effort to propose innovative and cost competitive routes to producing biochemicals from a variety of feedstocks using cell free approaches. These routes will help reduce the current risk and cost associated with classical cell free production. Cell free technologies show promise for application to the production of toxic/inhibitory products or products difficult to separate from microbial growth media and can help reduce the production barriers in multiple areas of biological conversion of feedstocks to biochemicals.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Cell Free and Immobilization Technologies (CFIT)

Today, several key factors negatively impact the production of fuels and chemicals from renewable sources. Common hindrances in the biological production of biochemicals are: (1) end-product or intermediate toxicity to the microbial biocatalyst, (2) the diversion of carbon to biomass formation, and (3) co-production of undesired byproducts. A particularly attractive alternative is to eliminate the biocatalyst entirely and instead operate the desired metabolic pathways in isolation, thus circumventing the roadblocks of biological toxicity, lower yields, and lack of specificity. However, cell-free enzyme systems still suffer from low productivities owing in part to the effects of free diffusion of intermediates, lack of long term enzyme stability, cofactor cost or inefficient recycling rates, and finally, the cost of enzyme production/purification. This project represents a new effort to propose innovative and cost competitive routes to producing biochemicals from a variety of feedstocks using cell free approaches. These routes will help reduce the current risk and cost associated with classical cell free production. Cell free technologies show promise for application to the production of toxic/inhibitory products or products difficult to separate from microbial growth media and can help reduce the production barriers in multiple areas of biological conversion of feedstocks to biochemicals. More specifically, we are developing new technologies and routes that could be used to produce high value biochemicals such as 2,3 BDO and terpenes (among many others) from biomass derived C5/C6 sugars or lignin but also from waste byproducts such as glycerol. This project will lead to significant innovation and also lead to new concepts and rational design of pathways and enzymes. Within this project, we will develop new metabolic enzyme cascades that will represent natural or artificial combinations of enzymes to produce the desired biochemicals from a variety of feedstocks. We are also developing basic design principals for constructing synthetic metabolons, using fusion proteins and synthetic protein scaffolds, to promote substrate channeling and stability while conserving peak activity. Additionally, our efforts include a techno economic analysis (TEA) of cell free approaches to provide the sensitivities of the process to enzyme loading, activity, pH, reactor volumes, cofactor recycling rates. Finally, we are focusing on further increasing stability, operating lifetime and efficiency of the pathway enzymes by immobilization on support surfaces. We are also focus on immobilizing pathway enzymes or combinations of enzymes on several different conducting polymers and evaluate the effect on stability and operating lifetime. As more combinations become available we will conduct a more systematic study of the means of immobilizing these enzymes. This preliminary work will enable the in-depth study of cofactor recycling at these interfaces using mediators for electron transfer. Taken together, these approaches will enable process intensification, continuous operation, lower capital and separations costs and end-product flexibility, and thus has the potential to contribute significantly to BETO's goals of cost competitive biofuels and bioproducts. To date we have demonstrated 1) the conversion of pyruvate to 2,3 BDO (4 enzymes with cofactor recycling, no additional cofactors needed) at >100g/L (>3g/L/h) using our enzyme tethering approach, 2) Generated mutants of a key redox enzyme with >180- fold improvement in NADH utilization over WT to >85% of NADPH utilization. 3) Produced mevalonate at >10g/L from glucose, limonene at >10g/L from mevalonate and more than >5g/L from glucose with crude enzyme preparations and complete cofactor recycling. 4) successfully generated fully active cross-linked aggregates (CLEAs) of NOX, a cofactor-regenerating water-forming oxidase that is key to our process with increased stability 5) Engineered and identified enzymes able to use the biomimetic cofactor NMN and synthesized new synthetic cofactors.

biocatalysis↗

Local microenvironment tuning induces switching between electrochemical CO 2 reduction pathways

Gas diffusion layers (GDL) have become a critical component in electrochemical CO 2 reduction (CO 2 R) systems because they can enable high current densities needed for industrially relevant productivity. Besides this function, it is often assumed that the choice of catalyst and electrolyte play much more important roles than the GDL in influencing the observed product selectivity. Here, we show that tuning of the GDL pore size can be used to control the local microenvironment of the catalyst and hence, effect significant changes in catalytic outcomes. This concept is demonstrated using sputtered Ag films on hydrophobic PTFE substrates with 6 different pore sizes. Although Ag is known to be a predominantly CO generating catalyst, we find that smaller pore sizes favor the generation of formate up to a faradaic efficiency of 43%. Combined experimental and simulation results show that this is due to the influence of the pore size on CO 2 mass transport, which alters the local pH at the electrode, resulting in reaction pathway switching between CO and formate. Importantly, our results highlight the importance of the local microenvironment as an experimental knob that can be rationally tuned for controlling product selectivity: a key consideration in the design of CO 2 R systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solar nebula chemistry - Implications for volatiles in the solar system

Current theoretical models of solar nebula chemistry which take into account the interplay between chemistry and dynamics are presented for the abundant reactive volatile elements including hydrogen, carbon, nitrogen, oxygen, and sulfur. Results of these models indicate that, in the solar nebula, the dominant carbon and nitrogen gases were CO and NO, whereas, in giant planet subnebulae, the dominant carbon and nitrogen gases were CH4 and NH3; in the solar nebula, the Fe metal grains catalyzed the formation of organic compounds from CO and H2 via the Fischer-Tropsch-type reaction. It was also found that, in solar nebula, bulk FeS formation was kinetically favorable, while FeO incorporation into silicates and bulk Fe3O4 formation were kinetically inhibited. Furthermore, clathrate formation was kinetically inhibited in the solar nebula, while it was kinetically favorable in giant planet subnebulae.

Fegley, Bruce, Jr.↗