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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 127 records · Page 7

Illinois Storage Corridor - CarbonSAFE Phase III: Policy, Regulatory, Legal and Permitting Characteristics; Subtask 5.5

The Illinois Storage Corridor (ISC) project aims to advance the commercial development and implementation of carbon capture and storage (CCS) technologies within a region in Illinois of suitable geology for carbon dioxide (CO 2 ) storage in deep saline aquifers. The project partners have annual emissions greater than 6.5 million tonnes per year; storage hubs are being explored at two sites—one near the One Earth Energy facility in east-central Illinois, and one near the Prairie State Generating Company campus in southwest Illinois. To implement the technology, legal, policy, and economic considerations must be explored. The United States Environmental Protection Agency (US EPA) administers the Underground Injection Control (UIC) program and is responsible for issuing Class VI permits to construct and operate CO 2 injection wells, i.e., a UIC Class VI well permit is required to inject CO 2 into the subsurface for geologic sequestration. The largest consideration of the Class VI well requirements is to protect underground sources of drinking water (USDWs). Additionally discussed are considerations for Class VI permits relating to public engagement. Besides permitting, property rights to storage sites, subsurface pore spaces, and areas for pipeline transportation must be secured. Pore space rights is still a novel concept being explored and not yet addressed by the Illinois legislature. It is believed that surface property rights are required for the subsurface pore space below, so long as there is not a separated mineral estate in the subsurface. Illinois legislature has addressed securing rights-of-way for CO 2 transportation, allowing for easements and the exercise of eminent domain to secure such rights. Economically, the incentives for CCS are ever-expanding. Recently, the federal government broadened the availability and increased the dollar-amounts for the § 45Q tax credits for geological storage of carbon oxides. Congress has also authorized the Advanced Industrial Facilities Development Program which allocates billions of dollars in funds to installing technology at industrial facilities to reduce greenhouse gas emissions. On the state level, Illinois has had its own incentives for CCS projects since 2009 and expanded its emission-related goals again in 2021. The law enacted in 2021 specifically creates a commission to explore implementing CCS at Prairie State Generating Company, a partner on the Illinois Storage Corridor project.

54 ENVIRONMENTAL SCIENCES↗

Enhanced methanol production from photothermal CO 2 reduction via multilevel interface design

Photothermal CO 2 hydrogenation is a promising route to produce methanol as a sustainable liquid solar fuel. However, most existing catalysts require a combination of solar irradiation and additional heat input to achieve a satisfactory reaction rate. For the few that can be driven solely by light, their reaction rates are one order of magnitude lower. We develop a photothermal catalyst with multilevel interfaces that achieves improved methanol production from photothermal CO 2 hydrogenation without external heat. The catalyst features a layered structure comprising Cu/ZnO/Al 2 O 3 (CZA) covered by oxidized carbon black (oCB), where the oCB/CZA interface promotes efficient heat generation and transfer, and the Cu/oxide interface contributes to high catalytic activity. Under a mild pressure of 8 bar, our oCB/CZA catalyst shows a methanol selectivity of 64.7% with a superior production rate of 4.91 mmol·g cza −1 ·h −1 , at least one order of magnitude higher than other photothermal catalysts solely driven by light. This work demonstrates a photothermal catalyst design strategy for liquid solar fuel production.

CO2 hydrogenation↗

Ch3MS-RF: a random forest model for chemical characterization and improved quantification of unidentified atmospheric organics detected by chromatography–mass spectrometry techniques

Abstract. The chemical composition of ambient organic aerosols plays a critical role in driving their climate and health-relevant properties and holds important clues to the sources and formation mechanisms of secondary aerosol material. In most ambient atmospheric environments, this composition remains incompletely characterized, with the number of identifiable species consistently outnumbered by those that have no mass spectral matches in the literature or the National Institute of Standards and Technology/National Institutes of Health/Environmental Protection Agency (NIST/NIH/EPA) mass spectral databases, making them nearly impossible to definitively identify. This creates significant challenges in utilizing the full analytical capabilities of techniques which separate and generate spectra for complex environmental samples. In this work, we develop the use of machine learning techniques to quantify and characterize novel, or unidentifiable, organic material. This work introduces Ch3MS-RF (Chemical Characterization by Chromatography–Mass Spectrometry Random Forest Modeling), an open-source, R-based software tool, for efficient machine-learning-enabled characterization of compounds separated in chromatography–mass spectrometry applications but not identifiable by comparison to mass spectral databases. A random forest model is trained and tested on a known 130 component representative external standard to predict the response factors of novel environmental organics based on position in volatility–polarity space and mass spectrum, enabling the reproducible, efficient, and optimized quantification of novel environmental species. Quantification accuracy on a reserved 20 % test set randomly split from the external standard compound list indicates that random forest modeling significantly outperforms the commonly used methods in both precision and accuracy, with a median response factor percent error of −2 %, for modeled response factors, compared to > 15 %, for typically used proxy assignment-based methods. Chemical properties modeling, evaluated on the same reserved 20 % test set and an extrapolation set of species identified in ambient organic aerosol samples collected in the Amazon rainforest, also demonstrate robust performance. Extrapolation set property prediction mean absolute errors for carbon number, oxygen to carbon ratio (O : C), average carbon oxidation state (OSc‾), and vapor pressure are 1.8, 0.15, 0.25, and 1.0 (log(atm)), respectively. Extrapolation set out-of-sample R2 for all properties modeled are above 0.75, with the exception of vapor pressure. While predictive performance for vapor pressure is less robust compared to the other chemical properties modeled, random-forest-based modeling was significantly more accurate than other commonly used methods of vapor pressure prediction, decreasing the mean vapor pressure prediction error to 0.24 (log(atm)) from 0.55 (log(atm)) (chromatography-based vapor pressure prediction) and 1.2 (log(atm)) (chemical formula-based vapor pressure prediction). The random forest model significantly advances an untargeted analysis of the full scope of chemical speciation yielded by two-dimensional gas chromatography (GCxGC-MS) techniques and can be applied to gas chromatography coupled with electron ionization mass spectrometry (GC-MS) as well. It enables the accurate estimation of key chemical properties commonly utilized in the atmospheric chemistry community, which may be used to more efficiently identify important tracers for further individual analysis and to characterize compound populations uniquely formed under specific ambient conditions.

54 ENVIRONMENTAL SCIENCES↗

Using respiration quotients to track changing sources of soil respiration seasonally and with experimental warming

Developing a more mechanistic understanding of soil respiration is hampered by the difficulty in determining the contribution of different organic substrates to respiration and in disentangling autotrophic-versus-heterotrophic and aerobic-versus-anaerobic processes. Here, we use a relatively novel tool for better understanding soil respiration: the apparent respiration quotient (ARQ). The ARQ is the amount of CO 2 produced in the soil divided by the amount of O 2 consumed, and it changes according to which organic substrates are being consumed and whether oxygen is being used as an electron acceptor. We investigated how the ARQ of soil gas varied seasonally, by soil depth, and by in situ experimental warming ( +4 ° C) in a coniferous-forest whole-soil-profile warming experiment over 2 years. We then compared the patterns in ARQ to those of soil δ 13 CO 2 . Our measurements showed strong seasonal variations in ARQ, from ≈0.9 during the late spring and summer to ≈0.7 during the winter. This pattern likely reflected a shift from respiration being fueled by oxidized substrates like sugars and organic acids derived from root and root respiration during the growing season to more reduced substrates such as lipids and proteins derived from microbial necromass during the winter. This interpretation was supported by δ 13 CO 2 values, which were lower, like lipids, in the winter and higher, like sugars, in the summer. Furthermore, experimental warming significantly changed how both ARQ and δ 13 CO 2 responded to soil temperature. Wintertime ARQ and δ 13 CO 2 values were higher in heated than in control plots, probably due to the warming-driven increase in microbial activity that may have utilized oxidized carbon substrates, while growing-season values were lower in heated plots. Experimental warming and phenology change the sources of soil respiration throughout the soil profile. The sensitivity of ARQ to these changes demonstrates its potential as a tool for disentangling the biological sources contributing to soil respiration.

59 BASIC BIOLOGICAL SCIENCES↗

Electrolyzer and method of use

Provided herein are methods for operating carbon oxide (CO x ) reduction reactors (CRR) and related apparatus. In some embodiments, the methods involve shutting off, reducing, or otherwise controlling current during various operation stages including hydration, break-in, normal operation, planned shut-offs, and extended shutoff or storage periods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Simultaneous reaction and separation of chemicals

The reaction rate of hydrocarbon pyrolysis can be increased to produce solid carbon and hydrogen by the use of molten materials which have catalytic functionality to increase the rate of reaction and physical properties that facilitate the formation and contamination-free separation of the solid carbon. Processes, materials, reactor configurations, and conditions are disclosed whereby methane and other hydrocarbons can be decomposed at high reaction rates into hydrogen gas and carbon products without any carbon oxides in a single reaction step. The process also makes use of specific properties of selected materials with unique solubilities and/or wettability of products into (and/or by) the molten phase to facilitate generation of purified products and increased conversion in more general reactions.

McFarland, Eric W.↗

Hydrothermally and thermally stable catalytic materials based on theta-alumina

A material and a method of making hydrothermally stable (catalytic) materials on the basis of theta-alumina support that is thermally and hydrothermally stable up to 1,150 C with metal, mixed metal-, metal-oxide nanoparticles dispersed upon it. Such materials did not lose significant amounts of their catalytic activity at temperature ranges for industrially relevant applications (including hydrocarbon oxidation, nitric oxide reduction, carbon monoxide oxidation) even after hydrothermal aging up to 1,150° C.

Khivantsev, Konstantin↗

Electrolyzer and method of use

Provided herein are methods for operating carbon oxide (CO x ) reduction reactors (CRR) and related apparatus. In some embodiments, the methods involve shutting off, reducing, or otherwise controlling current during various operation stages including hydration, break-in, normal operation, planned shut-offs, and extended shutoff or storage periods.

Source record↗

Thermal oxidation of nuclear graphite and pyrolytic carbon coatings

The oxidation of pyrolytic carbon (PyC) deposited via fluidized bed chemical vapor deposition was characterized and compared with that of standard nuclear-grade graphite. The materials were heated at 700 to 1000 °C in a thermogravimetric analysis system under 20% v/v O 2 flow, allowing for direct comparison of dynamic oxidative mass change in each material. Further, three different PyC samples fabricated under different conditions exhibited variation in total mass loss and mass loss rate, varying by as much as 709 mg/cm 2 in total mass loss and 14.2 (mg/cm 2 )/min in mass loss rate at a single temperature. These variations highlight the correlation between PyC microstructure/defect density and oxidation susceptibility. Additionally, changes in the microstructure and composition between PyC and graphite were characterized via scanning electron microscopy and correlated to the mass loss results. The results of this work have implications toward the safety of tristructural isotropic (TRISO) and other coated particle fuels, especially under off-normal conditions, given the limited information that exists about the oxidation behavior of PyC.

36 MATERIALS SCIENCE↗

An additively-manufactured molten salt-to-supercritical carbon di-oxide primary heat exchanger for solar thermal power generation – Design and techno-economic performance

The design and techno-economic performance of a compact additively manufactured (AM) molten salt (MS)-to-supercritical carbon di-oxide (sCO2) primary heat exchanger (PHE) for solar thermal application is described. The PHE design consists of sCO2 flow through an array of microscale pin fins while the MS flows through mm-scale rectangular channels. Constraints imposed by AM using laser powder bed fusion method are considered in the design. Structural and fluid flow simulations are performed to arrive at a viable design of the core and headers. A simplified one-dimensional steady state model for the PHE is developed including the impact of surface roughness from the AM process. A process-based cost model is used to determine the tradeoff between thermofluidic design and manufacturing cost. A parametric study is performed using the thermo-fluidic and cost models to determine the set of geometrical and flow variables that result in high power density and low cost, while restricting the pressure drop on the sCO2 side to less than 2% of line pressure. Flow rates of MS and sCO2 were varied over heat capacity rate ratios ranging from 0.2 to 1. Results indicate that it is possible to design a low-pressure drop AM PHE with an effectiveness of 90% and a power density in excess of 10 MW/m3 (including headers). Fabrication of representative nickel superalloy specimens are shown to demonstrate that low-porosity parts with the requisite dimensional tolerance of PHE core can be generated.

14 SOLAR ENERGY↗

Low Cost, High Volume, Carbon Fiber Precursor for Plasma Oxidation

Light weighting with carbon fiber is critical to improving the energy efficiency of wind turbines, airplanes, and automobiles, but the high cost of carbon fiber continues to limit market growth and applications. Half of this cost is in the raw materials. For the carbon fiber market to reach the next level of adoption, the cost of both the raw materials and conversion must be reduced. This project considered the combination of low-cost, textile-grade precursors combined with the increased efficiency of plasma oxidation to greatly reduce the cost of carbon fiber. The primary objective of this project was to make industrial-grade carbon fiber (550 ksi tensile strength, 35 Msi tensile modulus) from textile-grade PAN precursors, something that cannot be achieved with conventional oxidation and to date has not been achieved with any technology. To accomplish this, the project team iteratively optimized the process conditions in the plasma oxidation and carbonization stages to maximize the tensile properties of the resultant carbon fibers. This involved implementing experimental designs for both stages, whereby process conditions (e.g. temperature) were varied and correlated to fiber properties. Samples of oxidized PAN fibers (OPFs) were prepared using a small pilot-scale plasma oxidation oven at 4XTechnologies (4XT). The thermal, chemical, and physical properties of OPF samples were analyzed by the University of Tennessee (UTK) and Oak Ridge National Laboratory (ORNL). The OPF samples were then converted to carbon fiber by subsequent low- and high-temperature carbonization using a lab-scale furnace at ORNL. The resultant carbon fibers were tested for tensile strength also at ORNL, and the results were fed back into the experimental design. Of the hundreds of carbon fiber samples produced over the course of the project, the best sample had an average break strength of 479 ksi and modulus of 33 Msi. While the best tensile properties achieved fell short of the final project targets of 550 ksi for break strength and 35 Msi for modulus, the team demonstrated the potential to produce industrial-grade carbon fiber using textile-grade precursors. The best performing fiber samples had tensile properties that are 87% of the goal for tensile strength and 94% of the goal for tensile modulus. With additional optimization work, it is likely that the targets could be achieved, since only a fraction of the process parameter space was explored during this project. 4XT and its affiliate (4M) have already secured funding through private equity, and there is a CRADA (Cooperative Research and Development Agreement) project currently underway with the Carbon Fiber Technology Center (CFTF) at ORNL to continue this research. Additionally, while not an original goal of the project, the carbon fibers for most samples had diameters >8.5μm. This is considerably larger than commercially available carbon fiber products, which can impart unique properties to the composites (e.g. increased compressive strength) and decrease manufacturing costs even further. Moreover, these fibers were oxidized with plasma oxidation using residence times ranging <60mins, which would be considered fast for normal diameter fibers, but it is as much as 5x faster when factoring in the diameter of the fibers.

36 MATERIALS SCIENCE↗

Impacts of ruthenium valence state on the electrocatalytic activity of ruthenium ion-complexed graphitic carbon nitride/reduced graphene oxide nanosheets towards hydrogen evolution reaction

Design and engineering of effective electrode catalysts represents a critical first step for hydrogen production by electrochemical water splitting. Nanocomposites based on ruthenium atomically dispersed within a carbon scaffold have emerged as viable candidates. In the present study, ruthenium metal centers are atomically embedded within graphitic carbon nitride/reduced graphene oxide nanosheets by thermal refluxing. Subsequent chemical reduction/oxidation leads to ready manipulation of the ruthenium valence state, as evidenced in microscopic and spectroscopic measurements, and hence enhancement/diminishment of the electrocatalytic activity towards hydrogen evolution reaction in both acidic and alkaline media. Further, this is largely ascribed to the increased/reduced contribution of the Ru valence electrons to the density of state near the Fermi level which dictates the binding and reduction of hydrogen. Results from this study highlight the significance of the valence state of metal centers in the manipulation and optimization of the catalytic performance of single atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon-doped metal oxide interfacial nanofilms for ultrafast and precise separation of molecules

Membranes with molecular-sized, high-density nanopores, which are stable under industrially relevant conditions, are needed to decrease energy consumption for separations. Interfacial polymerization has demonstrated its potential for large-scale production of organic membranes, such as polyamide desalination membranes. We report an analogous ultrafast interfacial process to generate inorganic, nanoporous carbon-doped metal oxide (CDTO) nanofilms for precise molecular separation. For a given pore size, these nanofilms have 2 to 10 times higher pore density (assuming the same tortuosity) than reported and commercial organic solvent nanofiltration membranes, yielding ultra-high solvent permeance, even if they are thicker. Owing to exceptional mechanical, chemical, and thermal stabilities, CDTO nanofilms with designable, rigid nanopores exhibited long-term stable and efficient organic separation under harsh conditions.

Science & Technology - Other Topics↗

Baltimore Ecosystem Study: Soil atmosphere fluxes of carbon dioxide, nitrous oxide and methane, 1998 - ongoing

The Baltimore Ecosystem Study (BES) established a network of long-term permanent biogeochemical study plots in 1998. These plots provide long-term data on vegetation, soil and hydrologic processes in the key ecosystem types within the urban ecosystem. The network of study plots includes forest plots (upland and riparian), chosen to represent the range of forest conditions in the area and grass plots (to represent home lawns). Plots are instrumented with lysimeters (drainage and tension) to sample soil solution chemistry, time domain reflectometry probes to measure soil moisture, dataloggers to measure and record soil temperature, and trace gas flux chambers to measure the flux of carbon dioxide, nitrous oxide and methane from soil to the atmosphere. Measurements of in situ nitrogen mineralization, nitrification and denitrification were made at approximately monthly intervals from Fall 1998 - Fall 2000. Detailed vegetation characterization (all layers) was done in summer 1998 and 2015. Data from these plots has been published in Groffman et al. (2006, 2009), Groffman and Pouyat (2009), Savva et al. (2010), Costa and Groffman (2013), Duncan et al. (2013), Waters et al. (2014), Ni and Groffman (2018), Templeton et al. (2019). Literature Cited Costa, K.H. and P.M. Groffman. 2013. Factors regulating net methane flux in urban forests and grasslands. Soil Science Society of America Journal 77:850 - 855. Duncan, J. M., L. E. Band, and P. M. Groffman. 2013. Towards closing the watershed nitrogen budget: Spatial and temporal scaling of denitrification. Journal of Geophysical Research Biogeosciences 118:1-5; DOI: 10.1002/jgrg.20090 Groffman PM, Pouyat RV, Cadenasso ML, Zipperer WC, Szlavecz K, Yesilonis IC,. Band LE and Brush GS. 2006. Land use context and natural soil controls on plant community composition and soil nitrogen and carbon dynamics in urban and rural forests. Forest Ecology and Management 236:177-192. Groffman, P.M., C.O. Williams, R.V. Pouyat, L.E. Band and I.C. Yesilonis. 2009. Nitrate leaching and nitrous oxide flux in urban forests and grasslands. Journal of Environmental Quality 38:1848-1860. Groffman, P.M. and R.V. Pouyat. 2009. Methane uptake in urban forests and lawns. Environmental Science and Technology 43:5229-5235. DOI: 10.1021/es803720h. Ni, X. and P.M. Groffman. 2018. Declines in methane uptake in forest soils. Proceedings of the National Academies of Science of the United States of America 115:8587-8590. Savva, Y., K. Szlavecz, R. V. Pouyat, P. M. Groffman, and G. Heisler. 2010. Effects of land use and vegetation cover on soil temperature in an urban ecosystem. Soil Science Society of America Journal 74:469-480. Templeton, L., M.L. Cadenasso, J. Sullivan, M. Neel and P.M. Groffman. 2019. Changes in vegetation structure and composition of urban and rural forest patches in Baltimore from 1998 to 2015. Forest Ecology and Management. In press. Waters, E.R., J.L. Morse, N.D. Bettez and P.M. Groffman. 2014. Differential carbon and nitrogen controls of denitrification in riparian zones and streams along an urban to exurban gradient. Journal of Environmental Quality 43:955–963.

Groffman, Peter M↗

Alkaline Ethanol Oxidation Reaction on Carbon Supported Ternary PdNiBi Nanocatalyst using Modified Instant Reduction Synthesis Method

Direct ethanol fuel cells (DEFC) still lack active and efficient electrocatalysts for the alkaline ethanol oxidation reaction (EOR). In this work, a new instant reduction synthesis method was developed to prepare carbon supported ternary PdNiBi nanocatalysts with improved EOR activity. Synthesized catalysts were characterized with a variety of structural and compositional analysis techniques in order to correlate their morphology and surface chemistry with electrochemical performance. The modified instant reduction synthesis results in well-dispersed, spherical Pd85Ni10Bi5 nanoparticles on Vulcan XC72R support (Pd85Ni10Bi5/C(II-III)), with sizes ranging from 3.7 +/- 0.8 to 4.7 +/- 0.7 nm. On the other hand, the common instant reduction synthesis method leads to significantly agglomerated nanoparticles (Pd85Ni10Bi5/C-(I)). EOR activity and stability of these three different carbon supported PdNiBi anode catalysts with a nominal atomic ratio of 85:10:5 were probed via cyclic voltammetry and chronoamperometry using the rotating disk electrode method. Pd85Ni10Bi5/C-(II) showed the highest electrocatalytic activity (150 mA.cm(-2); 2678 mA.mg(-1)) with low onset potential (0.207 V) for EOR in alkaline medium, as compared to a commercial Pd/C and to the other synthesized ternary nanocatalysts Pd85Ni10Bi5/C-(I) and Pd85Ni10Bi5/C-(III). This new synthesis approach provides a new avenue to developing efficient, carbon supported ternary nanocatalysts for future energy conversion devices. The modified instant reduction method for synthesis of ternary Pd85Ni10Bi5/C-(II) nanocatalyst using Vulcan XC72R as carbon support initiates an agglomeration reduction, provides low average particle size, and enables enhanced activity for the alkaline ethanol oxidation reaction (EOR) compared to the common instant reduction method and to a commercial Pd/C catalyst.

Alkaline direct ethanol fuel cell↗

Graphene oxide precursor effects on 3D-printed carbon scaffolds

Manganese oxide (MnO 2 ), an earth-abundant material, is a promising component for energy storage devices, with uses in both pseudocapacitors and batteries. However, high MnO 2 loading often leads to reduced performance due to poor ion diffusion. 3D printing, particularly using the direct ink writing (DIW) technique, offers a solution by enabling the fabrication of electrodes with hierarchical porous structures and open channels that enhance mass transport and ion diffusion. Previous work demonstrated that 3D-printed graphene aerogels with MnO 2 coatings exhibited excellent electrochemical performance, even with thick electrodes, due to their optimized structure. Building on this work, the current study investigates the performance differences between aerogels developed using graphene oxide (GO) and reduced graphene oxide (rGO) as carbon precursors. Both materials were incorporated into thixotropic inks, 3D-printed into lattice structures, and carbonized. Despite expected similarities between the final graphene aerogel, rGO-based aerogels exhibited superior areal capacitance, compared to GO-based aerogels. These differences are attributed to the lower oxygen content and defect density of rGO, which influence its interaction with cellulose viscosifiers in the ink formulation. Brunauer–Emmett–Teller (BET) surface area analysis revealed that rGO aerogels exhibit a larger surface area and mesoporous structure, further enhancing their performance. When coated with MnO 2 , rGO-based aerogels maintained their superior capacitive behavior over GO-based aerogels. This study highlights the effect of carbon precursor on the end performance of graphene aerogels.

Materials science↗