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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 739 records · Page 41

Carbon Utilization: Electrochemical Approach Using Novel Catalyst and System Integration

The environmental footprint from power generation can be mitigated by capturing emitted carbon dioxide (CO2) and converting it to value-added fuel sources. A multitude of different fuels can be produced from CO2 depending on the chemical reaction catalysts. Typically, these pathways can be developed electrochemically, or through hydrogenation. In recent years the electrochemical reduction of CO2 has grown exponentially, as it has shown potential to decrease atmospheric pollution and provide an additional means of on-demand electricity storage. Formic acid (FA) in particular has industrial applications such as in fuel cells or as a hydrogen storage medium, and requires a lower thermodynamic energy input than any other fuel produced for electrochemical CO2 reduction. However, product selectivity remains a challenge for conventional electrocatalysts, making FA production efficiencies above 50% difficult. To address the challenge of catalytic selectivity, UK CAER employs enzymatic catalysts to facilitate the FA production and minimize unwanted byproducts. Our process couples the catalyst with a charge mediator which is necessary to shuttle electrons, and an electrolyte pH buffer to prevent the catalyst from degrading. Presently, production efficiencies have approached 60% at a rate of over 10 mM FA/hour. System design considerations (flow rate, bulk volume) will also be discussed.

01 COAL, LIGNITE, AND PEAT↗

Abstract for CRADA between Mati Car bon PBC and NETL

The National Energy Technology Laboratory (NETL) will assist Mati Carbon PBC (participant) in the design and execution of their community benefits plan (CBP) for scaling Enhanced Rock Weathering (ERW) carbon dioxide removal (CDR) in Arkansas. ERW involves spreading finely crushed rocks in agricultural fields to speed up the dissolution and release of certain minerals that amend soil acidity, replenish soil nutrients, and simultaneously converting CO 2 from the atmosphere to Dissolved Inorganic Carbon (DIC). ERW not only removes CO 2 from the atmosphere but also has the potential to generate co-benefits for famers through cost reductions and increased crop yields. The collaboration between NETL and Mati Carbon, PBC (participant) will entail a detailed review of the economic, environmental and community impact of ERW in agricultural settings. This review will guide all project related decisions. It will provide a better understanding of the scale of these potential co-benefits and quantify community needs that ERW can address.

54 ENVIRONMENTAL SCIENCES↗

The role of transition metal formyl intermediates in the reduction of CO and CO 2

Transition-metal formyl (metalloformyl) complexes occupy a central position in the activation of small molecules, particularly in the reduction of carbon monoxide (CO) and carbon dioxide (CO 2 ). This review examines five decades of progress in the synthesis of metalloformyl complexes and investigations into their structure and reactivity. The bonding in the M–CHO unit is best described as a resonance hybrid between a classical σ-bound formyl ligand and an oxycarbene-like electronic structure, which governs their distinctive spectroscopic signatures and versatile reactivity. Established synthetic routes are summarized, including pathways involving hydride addition and CO insertion, alongside a discussion of the thermodynamic and kinetic factors that control formyl stability. Decomposition pathways and Lewis-acid stabilization strategies are analyzed as key design principles for extending metalloformyl lifetimes under catalytic conditions. Particular attention is given to hydride transfer processes and the role of metalloformyl intermediates as both reactive substrates and hydride sources in reduction chemistry. Lastly, emerging catalytic strategies that exploit metalloformyl intermediates in CO 2 and CO reduction are evaluated, highlighting how control of hydricity, redox potential, and secondary-sphere interactions enables selective C—H bond formation under comparatively mild conditions. Collectively, these studies establish metalloformyl complexes as mechanistically informative and functionally relevant intermediates that bridge fundamental organometallic chemistry with modern approaches to small-molecule activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into the Electrochemical Oxidation and Reduction of Nickel Oxide Surfaces

Surface oxidation/reduction processes, driven by varying electrochemical potentials, can substantially impact catalyst effectiveness and, consequently, electrolyzer performance. Here, this study combines theoretical and experimental approaches to explore the surface redox behavior of nickel oxides, which are cost-effective and efficient catalysts for many electrochemical reactions. Surface Pourbaix diagrams for three different phases of nickel oxides, i.e., nickel hydroxide (Ni(OH) 2 ), nickel oxyhydroxide (NiOOH), and nickel dioxide (NiO 2 ), were constructed using density functional theory-based simulations. Various experimental methods, including cyclic voltammetry, in situ Raman spectroscopy, and electrochemical titration, were employed to probe the surface redox processes of nickel oxide thin films. Our findings indicate that the ABAB stacking sequence of Ni(OH) 2 lacks stability under oxidizing conditions to host the surface oxidation (deprotonation) events, while the AABBCC stacking sequence of NiOOH is energetically favorable due to the presence of interlayer hydrogen bonding. Rapid charge transfer facilitated by interlayer hydrogen bonding accounts for the higher reactivity of partially oxidized/reduced NiOOH (001) surfaces compared to Ni(OH) 2 (001) and NiO 2 (001) surfaces with the same stoichiometry, where interlayer hydrogen bonding is absent. Insights presented in this work can offer guidelines for optimizing operational conditions and tailoring the surface structures and oxidation states of nickel oxides to enhance performance in applications such as electrocatalysis and supercapacitors.

36 MATERIALS SCIENCE↗

Acetyl-CoA Synthesis Through a Bicyclic Carbon-Fixing Pathway in Gas-Fermenting Bacteria

Gas-fermenting acetogens can upgrade one-carbon (C1) compounds (such as CO2 and CO) to the two-carbon (C2) metabolite acetyl coenzyme A (CoA) and convert sugar feedstocks to acetyl-CoA with minimal CO2 emissions. Fulfilling the biosynthetic potential of these microbes requires overcoming challenges in pathway engineering. Here we design a synthetic acetyl-CoA bi-cycle-in addition to the natural carbon-fixing pathways-for C2 metabolite synthesis. This pathway produces an acetyl-CoA by fixation of two CO2 equivalents via three functional modules acting in sequence: carbon fixation, gluconeogenesis and non-oxidative glycolysis. The pathway was examined by in silico thermodynamic and kinetic analyses. The prototypic pathway was implemented in a syngas-fermenting organism, Clostridium ljungdahlii DSM 13528, by expressing a heterologous phosphoketolase that can work with other native enzymes in the host acetogen. The carbon conversion pathway is possible under various growth conditions and is independent of the Wood-Ljungdahl pathway for the valorization of H2 and CO2. This study reports the improvement of carbon conversion using a reductive acetyl-CoA bi-cycle and the potential impact of redox homoeostasis in the acetogenic host for industrial applications of gas fermentation.

Acetyl-CoA↗

Thermodynamic Theory of Proximity Ferroelectricity

Proximity ferroelectricity has recently been reported as a new design paradigm for inducing ferroelectricity, where a nonferroelectric polar material becomes a ferroelectric one by interfacing with a thin ferroelectric layer. Strongly polar materials, such as AlN and ZnO, which were previously unswitchable with an external field below their dielectric breakdown fields, can now be switched with practical coercive fields when they are in intimate proximity to a switchable ferroelectric. Here, we develop a general Landau-Ginzburg theory of proximity ferroelectricity in multilayers of nonferroelectrics and ferroelectrics to analyze their switchability and coercive fields. The theory predicts regimes of both “proximity switching,” where the multilayers collectively switch, and “proximity suppression,” where they collectively do not switch. The mechanism of the proximity ferroelectricity is an internal electric field determined by the polarization of the layers and their relative thickness in a self-consistent manner that renormalizes the double-well ferroelectric potential to lower the steepness of the switching barrier. Further reduction in the coercive field emerges from charged defects in the bulk that act as nucleation centers. The application of the theory to proximity ferroelectricity in Al x−1⁢ Sc x ⁢N/AlN and Zn 1−x ⁢Mg x ⁢O/ZnO bilayers is demonstrated. The theory further predicts that dielectric-ferroelectric and paraelectric-ferroelectric multilayers can potentially lead to induced ferroelectricity in the dielectric or paraelectric layers, resulting in the entire stack being switched, an exciting avenue for new discoveries. This thawing of “frozen ferroelectrics,” paraelectrics, and potentially dielectrics with high dielectric constants promises a large class of new ferroelectrics with exciting prospects for previously unrealizable domain-patterned optoelectronic and memory technologies.

36 MATERIALS SCIENCE↗

Utilizing biochars to stabilize mercury in contaminated floodplain sediment: Implications on mercury remediation

Major weather events contribute to the mobility and remobilization of legacy mercury (Hg) contamination and sequestration within sediments. Remediation using biochar as a soil amendment is a useful technique to immobilize and decrease Hg toxicity. This study explored whether biochar application is effective at stabilizing labile mercury (LaHg) from floodplain sediment. Controlled mesocosms simulating contamination events and flooding conditions were conducted. Floodplain sediment, which experiences annual periodic flooding, was collected. Sediment was spiked with inorganic Hg, applied with different types of biochar, and experienced simulated flooding events. Four types of biochar, pure rice husk (RH), pure peanut hull (PH), sulfur-modified rice husk (SMRH), and sulfur-modified peanut hull (SMPH), were applied at 10 and 40 g/kg rates (i.e., RH 10, RH 40; PH 10, PH 40, SMRH 10, SMRH 40, SMPH 10, SMPH 40). Total Hg, methylmercury, and LaHg concentrations were analyzed by coupling with redox potential measurements. Results indicate that SMRH 10, PH 10, PH 40, SMPH 10, and SMPH 40 successfully remediate Hg by stabilizing and reducing LaHg species from floodplain sediment. However, a high Hg methylation potential was observed with unsulfated and sulfated peanut hulls (PH 10, PH 40, SMPH 10, and SMPH 40), as they tend to create a reducing microenvironment that favors sulfate reduction reactions. Additionally, sulfur-modified biochar tends to promote Hg methylation potential at high application rates (i.e., 40 g/kg). We thus recommend using SMRH at a relatively low application rate (SMRH 10) for the remediation of Hg from floodplain sediment.

54 ENVIRONMENTAL SCIENCES↗

Assessing the methane mitigation potential of innovative management in US rice production

Abstract Rice is an important global crop while also contributing significant anthropogenic methane (CH 4 ) emissions. To support the future of rice production, more information is needed on the impacts of sustainability-driven management used to grow rice with lower associated methane emissions. Recent support for the impacts of different growing practices in the US has prompted the application of a regional methodology (Tier 2) to estimate methane emissions in different rice growing regions. The methodology estimates rice methane emissions from the US Mid-South (MdS) and California (Cal) using region-specific scaling factors applied to a region-specific baseline flux. In our study, we leverage land cover data and soil clay content to estimate methane emissions using this approach, while also examining how changes in common production practices can affect overall emissions in the US. Our results indicated US rice cultivation produced between 0.32 and 0.45 Tg CH 4 annually, which were approximately 7% and 42% lower on average compared to Food and Agriculture Organization of the UN (FAO) and US Environmental Protection Agency (EPA) inventories, respectively. Our estimates were 63% greater on average compared to similar methods that lack regional context. Introducing aeration events into irrigation resulted in the greatest methane reductions across both regions. When accounting for differences between baseline and reduction scenarios, the US MdS typically had higher mitigation potential compared to Cal. The differences in cumulative mitigation potential across the 2008–2020 period were likely driven by lower production area clay content for the US MdS compared to Cal. The added spatial representation in the Tier 2 approach is useful in surveying how impactful methane-reducing practices might be within and across regions.

Environmental Sciences & Ecology↗

Cooperative lane control application for fully connected and automated vehicles at multilane freeways

Advances in communications technology have made the development of connected and automated vehicle (CAV) applications that may potentially replace traditional, gantry operated lane control signals (LCSs) possible. Here, we develop the concept of a prototype CAV-enabled LCS application and provides a preliminary assessment of the potential improvement it offers over traditional LCS. Real-world data obtained from an LCS on I-66 in Northern Virginia was used to calibrate and validate a baseline simulation model. Further, the current lane control scenarios utilized in the Northern Virginia LCS were identified and relevant data resulting from implementation of those scenarios were collected to model the LCS in a simulation environment. The performance of real-world LCS was then compared to a prototype CAV-enabled LCS application developed in this research. The CAV-enabled LCS application consistently outperformed the traditional LCS with increased throughput and speeds. On average, an increase of 18.4%, 9.6% and 12.8% in throughput was observed for three selected scenarios under the best case of a 1 sec headway. Furthermore, the CAV-enabled LCS application was also found to reduce volatility, represented by variation in acceleration and deceleration regimes, by an average of 25.6% and 49.6%. The reduction in turbulence in the traffic stream may indicate potential improved safety with the CAV system.

33 ADVANCED PROPULSION SYSTEMS↗

Ozone pollution reduction partially offsets the negative impact of climate change mitigation efforts on global hunger

Studies warning of the potential negative effects of climate mitigation on food security through the competing use of land for bioenergy and afforestation have overlooked the impact of reduced ozone and its potential enhancement of crop yields. Here we use six global agro-economic models to compare the impacts of climate change with climate mitigation policy and ozone reduction on agriculture. We find that ozone reduction could reduce the negative impact of a 1.5 °C-consistent climate change mitigation policy on global hunger by 15% in 2050. Sub-Saharan Africa and India, where hunger is most severe, account for 56% of this global reduction. Our findings indicate that the negative effects of climate mitigation on global hunger could be partially offset by the ozone reduction impact.

54 ENVIRONMENTAL SCIENCES↗

High-coercivity ThMn 12 -type monocrystalline Sm–Zr–Fe–Co–Ti particles by high-temperature reduction diffusion

The ThMn 12 -type (Sm,Zr)1(Fe,Co,Ti) 12 compounds have the potential of powerful permanent magnets. Magnetically hard and anisotropic powders of such compound have been prepared by subjecting elemental oxides and Co mixed with Ca and CaO dispersant to a succession of high-energy ball-milling, reduction diffusion at 990–1220 °C and repeated washing. The size of the resulting ThMn 12 -type crystallites, their coercivity and fraction of monocrystalline particles were all found to increase with the reduction-diffusion temperature. Particles synthesized at 1220 °C were highly monocrystalline with a mean size of 0.54 μm and, after a magnetic-field alignment, exhibited a coercivity of 1.26 T and a full-density-projected maximum energy product of at least 209 kJ/m 3 (26.3 MGOe). Here, the strong positive effect of the reduction-diffusion temperature on the coercivity has been attributed to separation of the crystallites and to decrease in the incidence of structural defects.

36 MATERIALS SCIENCE↗

Characterizing Sustained Solar-to-Hydrogen Electrocatalysis at Low Cell Potentials Enabled by Crude Glycerol Oxidation

Unassisted solar-driven water electrolysis as a sustainable source for H 2 is limited by the high overpotential necessary to drive the oxygen evolution reaction (OER). Crude glycerol is an extremely alkaline byproduct of biodiesel synthesis that can be valorized or refined to produce more desirable chemicals. Glycerol can also be directly oxidized on an anode, replacing water oxidation, to reduce the applied cell potential requirements of electrolytic H 2 production or CO 2 reduction. An advantage of oxidizing glycerol in its crude form is the opportunity to valorize it without initial refinement. We describe an approach to replace the OER half-reaction with the sacrificial crude glycerol electrooxidation on a layered Au–Pt–Bi electrocatalyst on a Ni substrate. Compared to compositions with fewer components, the AuPtBi–Ni electrocatalyst improved the duration of performance and reduced the overall cell potential for glycerol electrooxidation in the extreme alkaline solutions representative of crude glycerol. These enhancements facilitated extended, unassisted hydrogen evolution from crude glycerol electrolysis, even under the power of a single-junction silicon solar cell at less than 1 sun illumination. We characterized the oxidation products of crude glycerol electrolysis and the subsequent products formed spontaneously in the electrolyte in the highly alkaline solution. This analysis helps to both identify the stoichiometric limits of glycerol oxidation at the low cell potentials of interest here and to understand the chemical control imparted by electrocatalysis on the ultimate compounds formed in the crude solution. Furthermore, the results for the AuPtBi electrocatalyst show that incorporating crude glycerol oxidation into integrated electrochemical systems can simultaneously simplify their design and significantly improve solar-to-hydrogen rates.

08 HYDROGEN↗

A survey study on arsenic speciation in coal fly ash and insights into the role of coal combustion conditions

Coal fly ashes (CFAs) are the low-density byproducts of the coal combustion process. Improper or uncontrolled CFA disposal poses significant environmental and health concerns due to the potential leaching of toxic heavy metals such as arsenic (As). Previous studies have investigated the content and speciation of As in different CFA samples, yet systematic information on As speciation in CFA with representative coal source and combustion conditions is still missing. Based on a recent survey study on the typical coal sources and combustion conditions across the U.S., this study selected 19 representative CFA samples to systematically investigate As speciation and potential correlations with these parameters. The composition, morphology, mineralogy, and As speciation of these CFA samples were characterized by complementary analytical, microscopic, and spectroscopic techniques. Synchrotron X-ray spectroscopy and microscopy analyses revealed the dominant As oxidation state to be As(V) and with strong associations to Ca, with the exception of 3 samples that had 19–51% As(III), likely due to the use of selective catalytic reduction (SCR) process. Principal component analysis was conducted to identify potential correlations of As concentration and oxidation state with parameters such as major element content, loss on ignition (LOI), average particle size, coal source, and combustion condition. Al 2 O 3 and FeO content were found to capture a majority of the variability. Further, results from this study provide fundamental basis for understanding the correlations between coal source, combustion conditions, CFA characteristics, and As speciation, and providing insights for downstream beneficial utilization or disposal management.

01 COAL, LIGNITE, AND PEAT↗

Reduction of a Heme Cofactor Initiates N -Nitroglycine Degradation by NnlA

Linear nitramines are potentially carcinogenic environmental contaminants. The NnlA enzyme from Variovorax sp. strain JS1663 degrades the nitramine N-nitroglycine (NNG)—a natural product produced by some bacteria—to glyoxylate and nitrite (NO 2 –). Ammonium (NH 4 +) was predicted as the third product of this reaction. A source of nonheme Fe II was shown to be required for initiation of NnlA activity. However, the role of this Fe II for NnlA activity was unclear. This work reveals that NnlA contains a b-type heme cofactor. Reduction of this heme—either by a nonheme iron source or dithionite—is required to initiate NnlA activity. Therefore, Fe II is not an essential substrate for holoenzyme activity. Our data show that reduced NnlA (Fe II -NnlA) catalyzes at least 100 turnovers and does not require O 2 . Finally, NH 4 + was verified as the third product, accounting for the complete nitrogen mass balance. Size exclusion chromatography showed that NnlA is a dimer in solution. Additionally, Fe II -NnlA is oxidized by O 2 and NO 2 – and stably binds carbon monoxide (CO) and nitric oxide (NO). These are characteristics shared with heme-binding PAS domains. Furthermore, a structural homology model of NnlA was generated using the PAS domain from Pseudomonas aeruginosa Aer2 as a template. The structural homology model suggested His 73 is the axial ligand of the NnlA heme. Site-directed mutagenesis of His 73 to alanine decreased the heme occupancy of NnlA and eliminated NNG activity, validating the homology model. We conclude that NnlA forms a homodimeric heme-binding PAS domain protein that requires reduction for initiation of the activity.

59 BASIC BIOLOGICAL SCIENCES↗

Emerging Technologies for Decarbonizing Silicon Production

Abstract Silicon (Si) is an important material for alloying, solar photovoltaics, and electronics. However, current methods of producing silicon require energy consumption of around 11–13 kWh/kg Si and direct carbon emissions are 4.7–5 tons CO 2 per ton Si which conflicts with global efforts to limit climate change. In this work, we discuss several promising methods for reducing or eliminating carbon emissions from the silicon production process. Such methods include using biocarbon, integrating the current process with carbon capture and utilization/storage (CCU/CCS), metallothermic reduction, hydrogen reduction, and molten salt electrolysis. We present the positive aspects and challenges of each approach. Biocarbon coupled with CCU/CCS is the most industrially mature technology and can be carbon–neutral or -negative but is not carbon-free. Hydrogen directly reducing silicon dioxide is not thermodynamically favorable, but it may be viable to use hydrogen in conjunction with other processes to reduce emissions. Metallothermic and electrochemical methods of production are promising and have the potential to create high-purity silicon with no reduction-related carbon emissions but have only been demonstrated at lab scale. Economic viability will likely be the next determining factor for which technologies are more widely researched and implemented. Graphical Abstract

08 HYDROGEN↗

Multifunctional Catalysts for the Tandem Reactions of Oxygenates

Industrially-relevant catalytic reactions rarely consist of a simple sequence of elementary steps. Moreover, kinetic coupling of multiple reactions on a catalyst surface is highly desired for process intensification and improved energy efficiency for large scale chemical transformations. The shifting landscape of hydrocarbon chemical feedstocks in the US also motivates research on the selective conversion of more complex molecules. One desirable type of catalytic reaction is the reduction of carboxylic acids that are produced from biomass feedstocks to their corresponding alcohols. The proposed research explores the fundamental importance of hydrogen spillover on a multifunctional catalyst for carboxylic acid reduction with H 2 composed of metal particles coupled to metal oxide particles. Recent work has demonstrated the excellent performance of supported tungsten oxide clusters for carboxylic acid reduction, but only after they are promoted with a late transition metal such as palladium. Elucidating the active state of the catalyst and the associated reaction mechanism for acid reduction on that active state are the overall goals of the proposed project and successful completion will enable future design of efficient multifunctional catalysts. The critically important role of the metal promoter is hypothesized to be its ability to dissociate H2 and spillover atomic H to the support. Although hydrogen spillover is a well-recognized phenomenon in catalysis, its role in both catalyst activation and catalytic turnover are still unresolved. The study combined materials synthesis, characterization, reactivity testing, and molecular simulations, to explore the effect of hydrogen chemical potential on the formation of the active catalytic sites and on the steady state catalytic reduction of carboxylic acid. Varying the hydrogen chemical potential through modification of the gas conditions, support composition, and metal loading to modulated the structure and catalytic performance of the reducible metal oxide. Dual function catalysts containing supported Pd and WO x species co-located on a non-reducible carrier (silica) and a reducible carrier (titania) were synthesized and characterized by electron microscopy, temperature-programmed reduction, and chemisorption. Spectroscopic methods such as X-ray absorption and UV-vis were also used to evaluate the catalysts, which were used in the reduction of propionic acid to aldehyde and alcohol. Quantum chemical calculations, including ab initio phase diagrams provided molecular insights into the H spillover phenomenon.

09 BIOMASS FUELS↗

Regional MJO Modulation of Northwest Pacific Tropical Cyclones Driven by Multiple Transient Controls

The Madden–Julian Oscillation (MJO) is widely acknowledged for its ability to modulate Northwest Pacific tropical cyclones (TCs), but a complete understanding of the underlying mechanisms remains uncertain. Beyond established effects of the MJO's relative humidity envelope, other dynamical factors have recently been invoked via new genesis potential indices and high-resolution modeling studies. Here we revisit the ability of the MJO to modulate West Pacific TCs through a quasi-explicit cyclone downscaling strategy driven by composited observations, paired later with a genesis index to investigate regional drivers of modulation. In this work, we reveal two distinct spatial modes of TC modulation in which the MJO's dynamic and thermodynamic effects act in tandem to increase TCs. In the South China Sea, for instance, shear reductions associated with the MJO's circulation lead to increasing potential intensity ahead of the arrival of a positive humidity anomaly, all of which combine for an extended period of cyclogenesis favorability.

58 GEOSCIENCES↗

Demand-side solutions in the US building sector could achieve deep emissions reductions and avoid over $100 billion in power sector costs

Buildings are energy-intensive and a primary source of US end-use sector carbon emissions. Although building emissions today are 25% below their 2005 peak, far deeper reductions are needed to reach the US 2050 net-zero emissions goal. However, plausible decarbonization pathways that consider both buildings and their interactions with the power grid remain poorly understood. Here, we couple detailed modeling of building energy use and the grid to quantify building decarbonization potential and associated grid impacts. We find up to a 91% reduction in building CO 2 emissions from 2005 levels by 2050 using a portfolio of building efficiency, demand flexibility, and electrification measures alongside rapid grid decarbonization. Building efficiency and flexibility could generate up to $107 billion in annual power system cost savings by 2050, offsetting over a third of the incremental cost of full grid decarbonization. Our results underscore multiple benefits of demand-side solutions for deep decarbonization of US buildings.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗