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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Influence of soil depth, irrigation, and plant genotype on the soil microbiome, metaphenome, and carbon chemistry

ABSTRACT Climate change is causing an increase in drought in many soil ecosystems and a loss of soil organic carbon. Calcareous soils may partially mitigate these losses via carbon capture and storage. Here, we aimed to determine how irrigation-supplied soil moisture and perennial plants impact biotic and abiotic soil properties that underpin deep soil carbon chemistry in an unfertilized calcareous soil. Soil was sampled up to 1 m in depth from irrigated and planted field treatments and was analyzed using a suite of omics and chemical analyses. The soil microbial community composition was impacted more by irrigation and plant cover treatments than by soil depth. By contrast, metabolomes, lipidomes, and proteomes differed more with soil depth than treatments. Deep soil (>50 cm) had higher soil pH and calcium concentrations and higher levels of organic acids, bicarbonate, and triacylglycerides. By contrast, surface soil (0–5 cm) had higher concentrations of soil organic matter, organic carbon, oxidizable carbon, and total nitrogen. Surface soils also had higher amounts of sugars, sugar alcohols, phosphocholines, and proteins that reflect osmotic and oxidative stress responses. The lipidome was more responsive to perennial tall wheatgrass treatments compared to the metabolome or proteome, with a striking change in diacylglyceride composition. Permanganate oxidizable carbon was more consistently correlated to metabolites and proteins than soil organic and inorganic carbon and soil organic matter. This study reveals specific compounds that reflect differences in organic, inorganic, and oxidizable soil carbon fractions that are impacted by interactions between irrigation-supplied moisture and plant cover in calcareous soil profiles. IMPORTANCE Carbon is cycled through the air, plants, and belowground environment. Understanding soil carbon cycling in deep soil profiles will be important to mitigate climate change. Soil carbon cycling is impacted by water, plants, and soil microorganisms, in addition to soil mineralogy. Measuring biotic and abiotic soil properties provides a perspective of how soil microorganisms interact with the surrounding chemical environment. This study emphasizes the importance of considering biotic interactions with inorganic and oxidizable soil carbon in addition to total organic carbon in carbonate-containing soils for better informing soil carbon management decisions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Potential high-performance magnet materials: Co- and Al-alloyed Sm 2 Fe 17

Sm 2 Fe 17 has long been known as a potential high-performance magnet whose deficiencies—planar anisotropy and lower-than-optimal T c —can be remedied by nitrogen addition, but which presents synthesis difficulties. In this work, we apply first-principles calculations to search for alternative low-cost, high-performance permanent magnets in this family, by exploring simultaneous Fe and Al substitution. Specifically, the goal is to improve properties of Sm 2 Fe 14 Al 3 easy-plane magnet at the stoichiometric composition. Density functional theory calculations were executed for three series of compounds, i.e., Sm 2 (Fe 1-x Co x ) 14 Al 3 , Sm 2 (Fe 1-x Co x ) 15 Al 2 , and Sm 2 (Fe 1-x Cox) 16 Al. We find that substitution of Fe with 12–18 of Co in % Sm 2 Fe 14 Al 3 modifies the magnetic anisotropy type from easy plane to easy axis with a substantial anisotropy of 7.1 MJ/m 3 . We also demonstrate that the largest part of magnetic anisotropy is introduced by 4f Sm atom electrons. Thus the rotation of magnetic moment orientation from $\langle$$1\bar10$$\rangle$ to $\langle$111$\rangle$ is followed by an increase of the occupied 4f state number and, as a result, the orbital part of the magnetic moment of one of the Sm atoms. This increase of the occupied 4f state number at an energy ~ -4.3 eV results in a significant reduction of band structure energy. The substitution of Fe by Co does not significantly reduce the magnetization of the compound and keeps it slightly above 1 T. This combination of magnetic anisotropy and magnetization makes the compound a promising candidate for a permanent magnet.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Low-intensity frequent fires in coniferous forests transform soil organic matter in ways that may offset ecosystem carbon losses

The impact of shifting disturbance regimes on soil carbon (C) storage is a key uncertainty in global change research. Wildfires in coniferous forests are becoming more frequent in many regions, potentially causing large C emissions. Repeated low-intensity prescribed fires can mitigate wildfire severity, but repeated combustion may decrease soil C unless compensatory responses stabilize soil organic matter. Here, we tested how 30 years of decadal prescribed burning affected C and nitrogen (N) in plants, detritus, and soils in coniferous forests in the Sierra Nevada mountains, USA. Tree basal area and litter stocks were resilient to fire, but fire reduced forest floor C by 77% (-36.4 Mg C/ha). In mineral soils, fire reduced C that was free from minerals by 41% (-4.4 Mg C/ha) but not C associated with minerals, and only in depths ≤ 5 cm. Fire also transformed the properties of remaining mineral soil organic matter by increasing the proportion of C in a pyrogenic form (from 3.2% to 7.5%) and associated with minerals (from 46% to 58%), suggesting the remaining soil C is more resistant to decomposition. Laboratory assays illustrated that fire reduced microbial CO2 respiration rates by 55% and the activity of eight extracellular enzymes that degrade cellulosic and aromatic compounds by 40–66%. Lower decomposition was correlated with lower inorganic N (-49%), especially ammonium, suggesting N availability is coupled with decomposition. The relative increase in forms of soil organic matter that are resistant to decay or stabilized onto mineral surfaces, and the associated decline in decomposition suggest that low-intensity fires may promote mineral soil C storage in pools with long mean residence times in coniferous forests.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Versatile microbial communities rapidly assimilate ammonium hydroxide-treated plastic waste

Abstract Waste plastic presently accumulates in landfills or the environment. While natural microbial metabolisms can degrade plastic polymers, biodegradation of plastic is very slow. This study demonstrates that chemical deconstruction of polyethylene terephthalate (PET) with ammonium hydroxide can replace the rate limiting step (depolymerization) and by producing plastic-derived terephthalic acid and terephthalic acid monoamide. The deconstructed PET (DCPET) is neutralized with phosphoric acid prior to bioprocessing, resulting in a product containing biologically accessible nitrogen and phosphorus from the process reactants. Three microbial consortia obtained from compost and sediment degraded DCPET in ultrapure water and scavenged river water without addition of nutrients. No statistically significant difference was observed in growth rate compared to communities grown on DCPET in minimal culture medium. The consortia were dominated by Rhodococcus spp., Hydrogenophaga spp., and many lower abundance genera. All taxa were related to species known to degrade aromatic compounds. Microbial consortia are known to confer flexibility in processing diverse substrates. To highlight this, we also demonstrate that two microbial consortia can grow on similarly deconstructed polyesters, polyamides, and polyurethanes in water instead of medium. Our findings suggest that microbial communities may enable flexible bioprocessing of mixed plastic wastes when coupled with chemical deconstruction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Soil Biogeochemistry

Depending upon type and pedogenic stage, soils are subject to biotic and abiotic interactions of complex nature depending on type, nature and specific properties. Soil biogeochemistry involves the study of elemental cycling as mediated by complex and inseparable interactions between the biotic (living) and abiotic (non-living) components of soils. Human activities have substantially altered biogeochemical cycling of several key elements including carbon, nitrogen, phosphorus, potassium, and other secondary and minor nutrients over the past few decades, which, in turn, had serious environmental consequences. The present chapter outlines the soil biogeochemical investigations conducted within Indian subcontinent in both natural ecosystems and managed agricultural systems and addresses the state-of-the-art in order to understand the undergoing biogeochemical reactions. Here, we sought to clarify complex interactions generally occurred during biogeochemical transformations of an element (or compound) of interest within the type-specific soil. Further, we emphasized the importance of advancing our understanding of feedback loops in soil biogeochemical processes as altered by anthropogenic perturbations in tropical and sub-tropical soils of India. Overall, this chapter is broadly focused on the nutrient cycling, which is followed by more specific topics like “soil microbiology,” “soil biodiversity,” and “soil biotechnology.”

Sihi, Debjani↗
DOE OSTI2021

Optical and mass-spectral characterization of mixed-gas flowing atmospheric-pressure afterglow sources

Plasma-based ambient desorption/ionization (ADI) sources for mass spectrometry (MS) often use helium as the primary discharge gas due to the large reaction cross section of excited helium species with atmospheric gases, which ultimately leads to efficient reagent-ion formation. However, some studies have shown that mixed-gas plasmas provide unique advantages. For instance, our group showed that a helium-oxygen flowing atmospheric-pressure afterglow (He:O 2 -FAPA) source yielded enhanced ion signals for small polar analytes, but compounds with aromatic rings underwent chemical modification to produce pyrylium species. Here, it is shown that the addition of H 2 to the helium FAPA gas significantly decreased the reagent-ion signals, but analyte-ion signal was not affected to the same degree. In addition, mass spectra obtained with He:H 2 -FAPA were chemically cleaner with fewer ions stemming from analyte species and produced less oxidation of analytes. Addition of nitrogen increased the abundance of negative reagent ions (e.g., NO 2 - and NO 3 - ) which led to enhanced ion signal for RDX. To better understand these unique advantages of a mixed-gas FAPA, the impact of molecular-gas (O 2 , N 2 , or H 2 ) addition on the optical-emission spectra from the discharge was also measured. Spatially resolved emission was obtained from the anode- and negative-glow regions. In general, addition of small fractions (~0.1%) of molecular gases decreased helium and OH emission intensities. Atomic oxygen and hydrogen emission increased with the addition of O 2 and H 2 , respectively. Furthermore, emission characteristics of N 2 , N 2 + , and NO with respect to molecular gas composition on He-FAPA were measured. Finally, fundamental plasma parameters, such as OH rotational temperature (T rot ), were also calculated for these mixed-gas systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

ELASTOMERIC MICROVASCULAR SELF-HEALING MATERIALS

Damaged elastomeric diaphragms within pneumatic controllers used in the oil and gas industry lead to an unintended release of methane. Self-healing microvascular materials capable of healing various types of damage have been fabricated. These microvascular materials are designed to replace currently available commercial diaphragms found in pneumatic controllers and provide a solution to reduce unintended methane leaks. Poly(dimethylsiloxane) (PDMS) was used as the main matrix material, with additional testing conducted on polyurethane and flexibilised epoxy materials. Microvascular networks were implemented into the elastomeric membranes to act as ves- sels to deliver healing agents to the damaged areas. The complex, interdigitated channel networks were created using a 3D printed custom compounded filament composed of polylactic acid (PLA) and tin(II) oxalate. Two-part liquid casting polymers were poured around the channels into a mould to create samples with the scaffolding of the microvascular channels intact. Hollow microvascular networks were created by placing the samples within a vacuum oven at 250◦C which causes the thermal depolymerisation of PLA into its gaseous monomers. The manufactured materials were placed in test stands and pressurized using nitrogen gas to determine their healing and mechanical behaviour. Self-healing behaviour was demonstrated using PDMS matrix materials and healing chemistries within a pressure test cell. This test cell was designed to detect any damage to a sample by record- ing an outlet pressure. Damages including puncture holes, diagonal cuts and star-shaped central iv cuts were applied to the samples and a reduction in the outlet pressure was recorded for all sam- ples. A variation in channel spacing and diameter was studied to determine the optimal design of the microvascular network for self-healing performance. The mechanical performance of elastomeric membrane materials within a diaphragmatic pressurised stand was observed. Deformations and strains around the channels and channel inter- sections at the midplane of the materials were recorded using digital image correlation. Normal stresses were calculated using Hooke’s law and the material properties of the PDMS matrix. A reduction in leak rate, implying the success of self-healing, was recorded within manu- factured diaphragm samples tested within a commercial valve. PDMS is the favourable material when compared to polyurethane and flexibilised epoxy for creating

03 NATURAL GAS↗
DOE OSTI2024

Metal-to-insulator transition in oxide semimetals by anion doping

Dirac semimetals exhibiting nontrivial topological characteristics stand as exemplary parent compounds, offering great promise for the realization of novel electronic states. These materials also serve as a versatile platform for systematically investigating topological quantum phase transitions. In this study, we present compelling evidence of profound structural and transport phase shifts in a recently uncovered oxide Dirac semimetal, SrNbO3, achieved through effective in situ anion doping. Notably, a remarkable increase in resistivity of more than three orders of magnitude at room temperature is observed upon nitrogen-doping. The extent of electronic modulation in SrNbO3 is strongly correlated with the misfit strain, underscoring its phase instability to both chemical doping and crystallographic symmetry variations. Using first-principles calculations, we discern that elevating the level of nitrogen doping induces an upward shift in the conductive bands of SrNbO3-?N?. Consequently, a transition from a metallic state to an insulating state becomes apparent as the nitrogen concentration reaches a threshold of 1/3. This investigation sheds light on the potential of anion engineering in oxide Dirac semimetals, offering pathways for manipulating their physical properties. These insights hold promise for future applications that harness these materials for tailored functionalities.

Hong, Haitao↗
DOE OSTI2020

Polydentate ligands and their complexes for molecular catalysis

Embodiments of the present disclosure relate generally to novel achiral and chiral sulfur-, nitrogen- and phosphorus-containing ligands, designated as NNS-type, P(O)NS-type, PNS-type, SNNS-type, SNNP(O)-type, or SNNP-type polydentate ligands and transition metal complexes of these ligands, including iridium complexes having PNS-type and NNS-type ligands. The catalysts derived from these ligands and transition metal complexes may be used in a wide range of catalytic reactions, including hydrogenation and transfer hydrogenation of unsaturated organic compounds, dehydrogenation of alcohols and boranes, various dehydrogenative couplings, chemoselective hydrogenation of α,β-unsaturated alcohols, and other catalytic transformations.

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

Soil properties and biochemical composition of ground-dwelling bee nests in agricultural settings

Soils deliver underrecognized ecosystem services by supplying habitat for ground-dwelling pollinators, such as wild bees and other organisms, that pollinate 80% of insect-pollinated plants and play a critical role in securing resilient pollination provisions. Our objective is to identify soil properties of ground nesting bee nests in agricultural settings of western Oregon, USA. We confirmed ground nesting bee and sand wasp activity in 7 agricultural sites and 1 recreational park. Soils from 17 bee and sand wasp nests were analyzed for pH, particle size distribution, and carbon and nitrogen content. We visually confirmed that 8 of the nesting bees were sweat bees from the Halictidae family and identified a captured bee specimen as Lasioglossum (Dialictus) (Hymenoptera: Halictidae). We located 2 sites with sand wasps where specimens were identified as Cerceris and Bembix (Hymenoptera: Crabronidae). The organic matter composition of three soil samples scraped from the linings of active nests were assessed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The FTICR-MS results identified unknown lipid compounds in the nest soil samples, which we hypothesize are waterproofing lipids secreted to line cell walls. Bee nests occurred in slightly acidic, bare-ground soils with low rock/vegetation coverage, low organic carbon content (<1%), and exhibited significantly higher silt-plus-clay fractions (>75%) versus data published for bee nests in prior work. Our findings present important implications for textural controls on nest site selection in wet, cool environments and demonstrate the importance of integrating soil properties to improve our understanding of ground-dwelling organisms and associated soil habitats.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Atmospheric Gases as Quantitative Indicators of Urbanization Across Land-Use Gradients

The urban heat island (UHI) effect is a significant phenomenon characterized by higher surface temperatures in cities compared to surrounding rural areas. This change in the Earth's energy balance presents considerable challenges for urban populations, increasing heat exposure, straining energy infrastructure, and exacerbating health vulnerabilities. Quantifying UHI intensity is challenging due to blurred distinctions between urban and rural areas as land-use patterns evolve. To address this challenge, the present study builds on the framework established by Salvador et al. (2025) and investigates the use of atmospheric constituents, specifically volatile organic compounds (VOCs) and inorganic gases, as tracers of urbanization levels. A key improvement in this approach is the inclusion of a designated true rural site for comparison. Field measurements were conducted at two locations in the Southeastern United States during the summer of 2025. Inorganic gases were monitored continuously, while VOC samples were collected biweekly and analyzed using a proton transfer reaction time-of-flight mass spectrometer. The urban site exhibited elevated concentrations of anthropogenic inorganic gases, with carbon monoxide and nitrogen dioxide averaging 878 ppb and 17.99 ppb, respectively. In contrast, the rural site showed lower levels of these pollutants, 796 ppb for carbon monoxide and 12.46 ppb for nitrogen dioxide, while displaying higher concentrations of biogenic VOCs, including isoprene and monoterpenes at 1.24 ppb and 0.08 ppb, respectively. Extended mass spectral analyses revealed distinct chemical differences between the two sites, supporting the observed variability of major gases. Overall, these findings are consistent with our previous research and highlight the value of atmospheric constituents as effective indicators of urbanization, thereby improving our understanding of UHI dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Nitrogen increases early‐stage and slows late‐stage decomposition across diverse grasslands

1. To evaluate how increased anthropogenic nutrient inputs alter carbon cycling in grasslands, we conducted a litter decomposition study across 20 temperate grasslands on three continents within the Nutrient Network, a globally distributed nutrient enrichment experiment 2. We determined the effects of addition of experimental nitrogen (N), phosphorus (P) and potassium plus micronutrient (K μ ) on decomposition of a common tree leaf litter in a long-term study (maximum of 7 years; exact deployment period varied across sites). The use of higher order decomposition models allowed us to distinguish between the effects of nutrients on early- versus late-stage decomposition. 3. Across continents, the addition of N (but not other nutrients) accelerated early-stage decomposition and slowed late-stage decomposition, increasing the slowly decomposing fraction by 28% and the overall litter mean residence time by 58%. 4. Synthesis. Using a novel, long-term cross-site experiment, we found widespread evidence that N enhances the early stages of above-ground plant litter decomposition across diverse and widespread temperate grassland sites but slows late-stage decomposition. These findings were corroborated by fitting the data to multiple decomposition models and have implications for N effects on soil organic matter formation. For example, following N enrichment, increased microbial processing of litter substrates early in decomposition could promote the production and transfer of low molecular weight compounds to soils and potentially enhance the stabilization of mineral-associated organic matter. By contrast, by slowing late-stage decomposition, N enrichment could promote particulate organic matter (POM) accumulation. Such hypotheses deserve further testing.

Nutrient Network (NutNet)↗
DOE OSTI2022

Improved Moisture Management Technology for Eco-N-Control Fertilizer

Three fertilizer technologies to manage nitrogen (N) release rates in soil dominate the market today: 1) bulk controlled-release technologies, which use the intrinsic solubility properties of a N-organic co-polymer to control N release; 2) barrier-based controlled-release technologies, which use porous polymer or sulfur coatings as a physical barrier to control N release from encapsulated N nutrients; and 3) slow-release technologies, which use enzyme inhibitors to chemically slow down the transformation of N nutrients into ammonia (NH 3 ) or to temporarily reduce populations of bacteria in the soil that are responsible for converting ammonium (NH 4 + ) to highly soluble nitrates. These technologies are expensive and provide only limited control of N-release rates. Also, from another environmental perspective, synthetic polymer coatings do not decompose easily and will accumulate over time with continuous application of fertilizer. For most of the past two decades we have been developing the Eco-N-Control solid-nitride fertilizer technology, a type of bulk controlled-release technology. With Eco-N-Control, solid-nitride compounds weather like a mineral, slowly releasing N at a rate determined by their composition. Testing by an industrial collaborator, however, showed that earlier versions of Eco-N-Control released at 25% of the desired rate when deployed in unsaturated soils. The overall goal of the current project, therefore, was to strengthen our IP position and the potential for licensing of Eco-N-Control solid-nitride fertilizer technology by developing new ways to manage the level of moisture in contact with the fertilizer when applied to soil thereby ensuring the desired N-release rate. We achieved this goal by developing a biodegradable polymer cross-linking approach that substantially improved performance of our patented solid-nitride fertilizer. We found that cross-linking an environmentally friendly and biodegradable polymer with a mixture of solid nitrides, other N-nutrient compounds and other additives offers several advantages: 1) mechanical robustness of fertilizer beads, 2) chemical stability during storage, 3) maintenance of sufficient water content in the vicinity of the nitride, and 4) control of N-release rates. We also updated our N-release testing protocol to more realistically simulate the conditions found in soil. Finally, we filed an invention disclosure record to protect these new aspects of Eco-N-Control technology, which offers a potential way to lower both agricultural and industrial pollution by providing an efficient N-delivery mechanism to plants.

42 ENGINEERING↗
DOE OSTI2023

Plasma-Coupled Flow Reactor Studies of Low-Temperature Plasma Assisted Kinetics of Methanol Blended with CO2

Ignition technologies based on low-temperature plasmas (LTP) have the potential to operate next generation engines at elevated pressures and increased dilution limits promoting higher efficiencies. From a practical standpoint, research on LTP igniters has shown to enhance combustion and ignition, improve flame stability, and extend the dilution limits of combustion. All of the aforementioned gains are complemented with higher ignition efficiencies. However, the biggest challenge with incorporating this technology into engines is the knowledge gap of how exactly plasma chemistry effects can enhance the basic combustion phenomena. This coupled with the lack of validated kinetic mechanisms for plasma-combustion chemistry is the biggest obstruction to recognize efficient ignition, especially for application relevant fuels and biofuels. In order to comprehensively evaluate the effects of LTP on an oxygenated fuel specific system, this present study examines the kinetics of methanol plasma-assisted pyrolysis and oxidation using a custom-built plasma flow reactor (PFR). Experimental regimes are also further extended to understand the effects of adding CO2 to the mixture and its consequence on reaction kinetics. The PFR is installed with a dielectric-barrier discharge (DBD) configuration to induce LTP into the fuel mixture. Non-equilibrium plasmas are generated by high-voltage pulses (nearing 20 KV) administered by a plasma pulser at high-pulse repetition rates (up to 10 kHz). In order to better understand and isolate plasma chemistry and its effect on neutral chemistry, the experiments were carried out by heavily diluting reactive mixtures in nitrogen at near isothermal conditions. This suppresses the effect of exothermic reactions on chemistry allowing stable intermediates and products to be detected and quantified using ex-situ GC/MS diagnostic methods. Experiments were carried out at 0.5 atm pressure and over a wide range of temperatures from 523 K to 1203 K. Experimental results depicted the enhancement in intermediates production as well as overall lower temperatures required for complete fuel consumption in the plasma specific cases as opposed to their pure thermal counterpart. Formation of oxygenated and nitrile compounds specific to plasma assisted pyrolysis cases illustrated the efficacy of LTP to introduce new reaction pathways accelerating fuel decomposition. Increase in reactivity at lower temperatures is sought to be an effect induced by plasma chemistry postulating the acceleration in intermediates production. The onset of thermal ignition in plasma assisted oxidation is seen 200 K earlier than thermal oxidation highlighting efficient fuel conversion to final byproducts. Enhanced collisional processes afforded by LTP is seen to perturb reaction pathways between oxygenated fuel radicals and N-atoms to alter overall chemical reactivity. New insights into kinetics are gained from this study highlighting governing plasma assisted combustion (PAC) pathways for oxygenated fuel reaction chemistry. The results from this study can be used to develop future mechanisms specific to plasma chemistry which can bridge the mechanistic knowledge gap for LTP ignition so that future engines can adopt LTPs in their design for efficient combustion.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Understanding the Reactions Between Fe and Se Binary Diffusion Couples

Spurred by recent discoveries of high-temperature superconductivity in Fe-Se based materials, the magnetic, electronic, and catalytic properties of iron-chalcogenides have drawn significant attention. Furthermore, much remains to be understood about the sequence of phase formation in these systems. In this work, we shed light on this issue by preparing a series of binary Fe-Se ultrathin diffusion couples via designed thin film precursors and investigating their structural evolution as a function of composition and annealing temperature. Two previously unreported Fe-Se phases crystallized during the deposition process on a nominally room-temperature Si substrate in the 27-33% and 37-47% Fe (atomic percent) composition regimes. Both phases completely decompose after annealing to 200°C in a nitrogen glovebox. At higher temperatures, the sequence of phase formation is governed by Se loss in the annealing process, consistent with what would be expected from the phase diagram. Films rich in Fe (53-59% Fe) crystalized during deposition as β-FeSe (P4/nmm) with preferred c-axis orientation to the amorphous SiO 2 substrate surface, providing a means to non-epitaxial self-assembly of crystallographically aligned, iron-rich β-FeSe for future research. Our findings suggest the crystallization of binary Fe-Se compounds at room temperature via near diffusionless transformations should be a significant consideration in future attempts to prepare metastable ternary and higher order compounds containing Fe and Se.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Microbial Community Field Surveys Reveal Abundant Pseudomonas Population in Sorghum Rhizosphere Composed of Many Closely Related Phylotypes

While the root-associated microbiome is typically less diverse than the surrounding soil due to both plant selection and microbial competition for plant derived resources, it typically retains considerable complexity, harboring many hundreds of distinct bacterial species. Here, we report a time-dependent deviation from this trend in the rhizospheres of field grown sorghum. In this study, 16S rRNA amplicon sequencing was used to determine the impact of nitrogen fertilization on the development of the root-associated microbiomes of 10 sorghum genotypes grown in eastern Nebraska. We observed that early rhizosphere samples exhibit a significant reduction in overall diversity due to a high abundance of the bacterial genus Pseudomonas that occurred independent of host genotype in both high and low nitrogen fields and was not observed in the surrounding soil or associated root endosphere samples. When clustered at 97% identity, nearly all the Pseudomonas reads in this dataset were assigned to a single operational taxonomic unit (OTU); however, exact sequence variant (ESV)-level resolution demonstrated that this population comprised a large number of distinct Pseudomonas lineages. Furthermore, single-molecule long-read sequencing enabled high-resolution taxonomic profiling revealing further heterogeneity in the Pseudomonas lineages that was further confirmed using shotgun metagenomic sequencing. Finally, field soil enriched with specific carbon compounds recapitulated the increase in Pseudomonas, suggesting a possible connection between the enrichment of these Pseudomonas species and a plant-driven exudate profile.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Natural Product Gene Clusters in the Filamentous Nostocales Cyanobacterium HT-58-2

Cyanobacteria are known as rich repositories of natural products. One cyanobacterial-microbial consortium (isolate HT-58-2) is known to produce two fundamentally new classes of natural products: the tetrapyrrole pigments tolyporphins A–R, and the diterpenoid compounds tolypodiol, 6-deoxytolypodiol, and 11-hydroxytolypodiol. The genome (7.85 Mbp) of the Nostocales cyanobacterium HT-58-2 was annotated previously for tetrapyrrole biosynthesis genes, which led to the identification of a putative biosynthetic gene cluster (BGC) for tolyporphins. Here, bioinformatics tools have been employed to annotate the genome more broadly in an effort to identify pathways for the biosynthesis of tolypodiols as well as other natural products. A putative BGC (15 genes) for tolypodiols has been identified. Four BGCs have been identified for the biosynthesis of other natural products. Two BGCs related to nitrogen fixation may be relevant, given the association of nitrogen stress with production of tolyporphins. The results point to the rich biosynthetic capacity of the HT-58-2 cyanobacterium beyond the production of tolyporphins and tolypodiols.

60 APPLIED LIFE SCIENCES↗