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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Realizing efficient operations of Ni-cermet-based fuel cells on hydrocarbons via an in situ self-assembled metal/oxide nano-heterostructured catalyst

Operating Ni-cermet-based fuel cells on hydrocarbons is charming by largely hindered by poor coking tolerance and severe deterioration. Here, in this study, we report an effective metal/oxide nano-heterostructured catalyst with a nominal composition of Pr 0.95 Ru 0.05 O 2-δ (PRO), which is in situ self-assembled to a Pr 0.95 Ru 0.05-x O 2-δ oxide frame coated with Ru metallic nanoparticles (denoted as Ru/PRO) under the operation condition. When applied to the Ni-cermet (Ni-YSZ) anodes, the cells achieve decent peak power densities of 1.784 and 1.870 W cm -2 on CH 4 and C 3 H 8 with only 3% H 2 O at 750 °C, respectively. Moreover, the cells with Ru/PRO-coated anode demonstrate excellent durability when operated on CH 4 for ~ 220 h and C 3 H 8 for ~115 h. It is demonstrated that the Ru/PRO generates hydroxyl species that react with carbon species, followed by the formation of COH intermediates on Ni anode surfaces for removing the coking, as confirmed by experiments and computations.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Black Swan Event Small-Sample Transfer Learning (BEST-L) and its Case Study on Electrical Power Prediction in COVID-19

The black swan event will usually cause a great impact on the normal operation of society. The scarcity of such events leads to a lack of relevant data and challenges in dealing with related problems. Different situations also make the traditional methods invalid. In this paper, a transfer learning framework and a convolutional neuron network are proposed to deal with the black swan small-sample events (BEST-L). Taking the COVID-19 as a typical black swan event, the BEST-L is utilized to achieve accurate mid-term load forecasting using the relationship between economy and electricity consumption. The experiment results show that the transfer learning model can effectively learn the basic knowledge about the relationship between the adopted input and output data and use a relatively small amount of data during the black swan event to improve the target areas' generalization. The approach and results can provide an effective approach to respond and react to sudden changes quickly and effectively in similar open problems.

black swan event↗
DOE OSTI2021

Systematic investigations on iron cycling in phosphorus/siderophore systems: Synergism or antagonism?

Synergisms between microbial exudates on Fe (hydr)oxide dissolution as an effective Fe acquisition pathway have been recently addressed and vigorously debated. However, Fe liberation mechanisms and where siderophores and phosphorus (P) coexist received little attentions. Current study systematically investigated ferrihydrite dissolution in the presence of desferrioxamine B (DFOB) (a kind of fungally-derived siderophores) and inorganic/organic phosphorus (orthophosphate, Pi; myo-inositol hexaphosphate, IHP), as a function of solute pH, reaction time and reagent content. Reacted solids were characterized by N 2 -BET adsorption, zeta (ζ) potential analysis, sequential extraction analysis (SEDEX), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), micro Raman spectroscopy and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). Our results indicate that upon reaction with P-only or (DFOB + P) systems, interfacial complexation partially switched from monolayer bidentate-binuclear surface complexes to ternary complexes, or laterally transformed into amorphous Fe–P precipitates. The Fe-Pi complex precipitated more readily under acidic conditions, and Fe-IHP complex preferentially nucleated in neutral-alkaline environments. Phosphorus slightly promoted Fe release from minerals and fixation to the leached layer or interfacial liquid zone initially, but subsequently prevented further attacks from protons and DFOB. The co-effects of P and DFOB likely correspond to two successive scenarios: 1) DFOB is preferentially attracted toward ferrihydrite surfaces by negative electrical fields induced by adsorbed phosphorus and can act synergistically with labile P–Fe complexes, resulting in intensive temporal dissolution of Fh; 2) subsequent Fe shuttling to DFOB can be prohibited by stabilized, passive P/Fe–P layers. Finally, our results emphasize the antagonism between P compounds and siderophores (i.e., DFOB here) on ferrihydrite dissolution to improve understanding of the biologically-mediated Fe cycling in natural systems.

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

The impact of mineral reactive surface area variation on simulated mineral reactions and reaction rates

Reactive transport modeling is an essential tool to simulate complex geochemical reactions in porous media that can impact formation properties including porosity and permeability. However, simulating these reactions is challenging due to uncertainties in model parameters, particularly mineral surface areas. Imaging has emerged as a powerful means of estimating model parameters including porosity and mineral abundance, accessibility and accessible surface area. However, these parameters, particularly mineral accessible surface area, vary with image resolution. This work aims to enhance understanding of the impact of image resolution and other means of estimating mineral reactive surface area on simulated mineral reactions and reaction rates. Mineral surface areas calculated from images with resolutions of 0.34 μm and 5.71 μm were used to simulate mineral reactions in the context of geologic CO 2 sequestration in the Paluxy formation at the continuum scale. Additional simulations were carried out using BET surface areas collected from the literature and geometric surface areas. Simulations were run for 7300 days and mineral volume fractions and effluent ion concentrations tracked and compared. Variations in mineral surface areas measured from images are within 1 order of magnitude and yield similar simulation results, indicating the impact of image resolution on simulated reactions and reaction rates is minimum for the resolutions and sample considered. In comparison, surface areas obtained from BET and geometric approaches are 1–4 orders of magnitude higher than image-obtained surface areas and result in greater simulated reaction rates and extents. Minerals with high reaction rates (calcite and siderite) are most impacted by surface area values at short times where simulated mineral volume fractions at longer times agree relatively well, even for simulations with several orders of magnitude variation in surface area. Phases with lower reaction rates, such as K-feldspar and muscovite, are predominantly impacted over longer times where variations in surface areas impact reaction extents and porosity evolution. Overall, variations in surface areas due to image resolution are small and result in little variation in simulated reactions and reaction rates while there are significant variations in simulation results when other surface area estimates are used. These variations, however, depend on the reactivity of the mineral phase where surface areas of fast-reacting phases largely impact simulations at short (hours to days) timescales and surface areas of slower-reactive phases impact longer term simulations (years).

58 GEOSCIENCES↗
DOE OSTI2020

Leak detection in a subcritical boiler

Thermal power plants experience cycling duty leading to the fatigue of the boiler and heat exchanger tubes. As a result, tube failures occur frequently in coal fired fleets leading to forced outages. Furthermore, because the tube leaks have been the major source of unwanted shutdowns and the number of outages is increasing, present work focuses on the detection and isolation of the leak in a subcritical boiler based upon the process data from a commercial coalfired power plant. The mass balance equation around the steam drum was analyzed using timeseries data collected from a 300 MW power plant. The ratio of the feed water mass flow rate to the steam mass flow rate was defined as a key parameter for detecting leaks. The difference in slope between the feedwater and steam mass flow rate during the normal and faulty operations was established as the upper control limit for real time monitoring. To reduce false alarm rates that arise when raw signal is directly compared against the threshold due to common process fluctuations, an optimal filter was derived for smoothing. It was found that the optimal filter reacted much more quickly to process changes than an exponential moving average filter, around 8 h earlier on average. Occurrence of relatively high false alarm rates even in the filtered responses was related to the cycling of the boiler from the base load condition. Variable threshold was established to keep false alarm rates to the minimum while maintaining the leak detection rate. Finally, the leak was located at the economizer and this could readily be isolated by investigating the magnitude of the mass flow rates ratio and the temperature at the economizer outlet.

42 ENGINEERING↗
DOE OSTI2024

Design and evaluation of a dilute flow particle-to-air heat exchanger for energy storage applications

The use of inert and redox-active particles for high-temperature energy storage requires the development of components that can efficiently transfer energy to high-pressure working fluids like supercritical carbon dioxide (sCO 2 ). Dilute flow reactors can enable high working fluid outlet temperatures and minimal parasitic losses compared to moving packed bed and fluidized bed reactors. This research uses both computational and experimental methods to explore the design trade-offs and practical challenges of a novel component for transferring energy from dilute flows of hot, reduced metal oxide (MO x ) particles to sCO 2 in tubes. A discretized thermal resistance network model, which accounts for particle hydrodynamics, multi-mode heat transfer, and reaction equilibrium, guides the design of a prototype device. This device is experimentally tested with a surrogate heat transfer fluids and inert particle temperatures up to 400°C and a heat duty exceeding 1 kW. The data are used to validate the thermal hydraulic sub-models, allowing for the simulation of reacting particle scenarios. Under nominal design conditions, the flow rate of reactive particles is predicted to be 30% lower than that of inert particles for the same energy recovered, with over 70% of the stored particle energy transferred to the sCO 2 . Furthermore, these findings can inform the design of more efficient energy recovery reactors for particle-based systems and can be integrated into system-level concentrated solar power models with thermal storage to optimize operating conditions.

14 SOLAR ENERGY↗
DOE OSTI2025

Investigation of fuel film formation and soot emissions in a GDI engine during cold-start with Split-injection strategies

This study investigates the impact of fuel-film formation on engine-out soot emissions in a gasoline direct injection (GDI) engine under cold-start conditions. Split-injection strategies were applied by varying the number of injections, injection duration, and total fuel quantity to affect wall wetting and control the average in-cylinder equivalence ratio. A combined experimental and numerical approach was employed to analyze fuel-film deposition, combustion efficiency, and engine-out soot and unburnt hydrocarbons (UHC) emissions. In particular, fuel film distribution estimated by means of non-reacting, 3-D, computational fluid dynamics (CFD) simulations, together with experimentally measured soot data, were used to investigate fuel film formation and its role in soot generation. In the experiments, a skip-fired engine control strategy was applied to mimic the transient nature of engine cold-start operation. The results indicate that, under the same total number of injections, increasing the average in-cylinder equivalence ratio through longer injection durations improves combustion stability, as indicated by the decrease of the coefficient of variation of IMEP n (Net Indicated Mean Effective Pressure) from 6.0 % to 0.6 %. However, this strategy leads to higher soot emissions, which increased by nearly an order of magnitude, primarily due to enhanced wall-film formation. In contrast, increasing the number of injections while maintaining a constant equivalence ratio significantly impacts fuel-film deposition and, consequently, soot emissions, with a fivefold reduction of the measured engine-out soot, decreasing from 3.5 mg to 0.7 mg. A soot-film correlation was developed and achieved a high coefficient of determination (r 2 = 0.95) and was further extended to account for spark timing effects. These findings confirm the effectiveness of split-injection for avoiding wall film formation and soot emissions, and the critical role of fuel film in soot generation, supporting the hypothesis that pool fires play a crucial role in contributing to soot formation under these cold-start conditions. In conclusion, the study also indicates the value of a predictive soot-film correlation for developing cold-start emission control strategies.

Engine Cold-start↗
DOE OSTI2020

Reaction of BCl 3 with H- and Cl-terminated Si(100) as a pathway for selective, monolayer doping through wet chemistry

The reaction of boron trichloride with the H and Cl-terminated Si(100) surfaces was investigated to understand the interaction of this molecule with the surface for designing wet-chemistry based silicon surface doping processes using a carbon- and oxygen-free precursor. The process was followed with X-ray photoelectron spectroscopy (XPS). Within the reaction conditions investigated, the reaction is highly effective on Cl-Si(100) for temperatures below 70°C, at which point both surfaces react with BCl$_3$. The XPS investigation followed the formation of a B 1s peak at 193.5 eV corresponding to (B-O)$_x$ species. Even the briefest exposure to ambient conditions lead to hydroxylation of surface borochloride species. However, the Si 2p signature at 102 eV allowed for a confirmation of the formation of a direct Si-B bond. Density functional theory was utilized to supplement the analysis and identify possible major surface species resulting from these reactions. This work provides a new pathway to obtain a functionalized silicon surface with a direct Si-B bond that can potentially be exploited as a means of selective, ultra-shallow, and supersaturated doping.

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

Thermal stability and protective properties of phenylphosphonic acid on Cu(111)

Phenylphosphonic acid (PPA) adsorbed on Cu(111) has been studied by synchrotron radiation-based techniques in combination with density functional theory calculations. Here, the dehydrogenated phenylphosphonic acid molecule (PP) strongly bound in a tridentate geometry through oxygen atoms to Cu(111) is shown to be the dominant surface species in the temperature range 150–300 °C. The stable PP adlayer substantially protects the Cu(111) surface from oxidation during exposure to ambient conditions. Thermal treatment of the PPA adlayer at 375 °C initiates molecular decomposition through several channels: P–O bond scission forming C 6 H 5 PO 2 ; C–P bond scission forming phenyl and PO 3 ; and C–H bond scission forming C 6 H 4 PO 3 . All three reaction steps have activation barriers of 1.7–1.8 eV. Small products such as O, H, and phenyl can immediately react further and desorb, while the remaining phosphonate species undergo condensation. After annealing at a higher temperature, the phosphonate group is further reduced from oxygen-rich to phosphorus-rich species, which form the majority of remaining adsorbates after 500 °C treatment.

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

A facile approach for site-selective and large-area growth of MoS 2 through heterogeneous nucleation

Heterogeneous nucleation could be an effective approach to producing an array of transition metal dichalco-genides (TMDs) at controlled locations on a substrate. In this study, we prepared Pt mesa structures on the substrate to induce heterogeneous nucleation of MoS 2 during chemical vapor deposition (CVD) and investigated the adsorption of nuclei using Monte Carlo (MC) simulations. The MC simulations suggest that the site-selectivity of MoS 2 dramatically drops when the CVD growth time goes beyond the critical time at which nuclei fully cover the Pt mesas, and such critical time can be delayed when the size of Pt mesas increases. Our experimental observations on a clean array of MoS 2 successfully synthesized on 10 um-width square Pt mesas but not on 4 um -width square Pt mesas support the MC simulation. We further designed a simple method employing dummy substrates to increase the yield of the site-selective MoS 2 array. Computational fluid dynamics (CFD) simulation reveals that such dummy substrates restrict the precursor concentration and provide a confined channel for the precursors to react slowly, which benefits producing large-area and site-selective MoS 2 . Furthermore, compared with conventional CVD, the total coverage of site-selective MoS 2 has enlarged by seven times using dummy substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Site-specific surface reactivity on SnO 2 : Evaluating selective atomic layer deposition processes

Area selective atomic layer deposition (AS-ALD) is a bottom-up synthesis approach with potential for deposition with molecular level precision. Here, the site-specific hydration of metal oxide substrates, combined with surface H 2 O-selective ALD processes, provides a potentially powerful path to targeted synthesis. Density functional theory (DFT) calculations are used to predict the thermodynamics of ALD precursor reactivity and hydration for (001), (101), (110), and (100) rutile SnO 2 facets as a function of temperature. Trimethylaluminum (TMA) and dimethyl aluminum isopropoxide (DMAI) dimers are predicted to react with both dehydrated and hydrated SnO 2 (001), (101), and (110) facets at ALD-relevant temperatures, while the SnO 2 (100) facet is predicted to be uniquely unreactive with TMA and DMAI monomers as well as dehydrate near 177 °C making this facet more amenable to targeted ALD. In situ ellipsometric studies of Al 2 O 3 ALD on polycrystalline SnO 2 at 150 °C are consistent with the computational predictions of rapid and unselective nucleation, in stark contrast to inhibited and selective ALD on isostructural rutile TiO 2 .

Atomic Layer Deposition↗
DOE OSTI2023

Intact mass spectrometry screening to optimize hydroxyl radical dose for protein footprinting

Hydroxyl radical protein footprinting (HRPF) using synchrotron radiation is a well-validated method to assess protein structure in the native solution state. In this method, X-ray radiolysis of water generates hydroxyl radicals that can react with solvent accessible side chains of proteins, with mass spectrometry used to detect the resulting labeled products. An ideal footprinting dose provides sufficient labeling to measure the structure but not so much as to influence the results. The optimization of hydroxyl radical dose is typically performed using an indirect Alexa488 fluorescence assay sensitive to hydroxyl radical concentration, but full evaluation of the experiment's outcome relies upon bottom-up liquid chromatography mass spectrometry (LC-MS) measurements to directly determine sites and extent of oxidative labeling at the peptide and protein level. A direct evaluation of the extent of labeling to provide direct and absolute measurements of dose and “safe” dose ranges in terms of, for example, average numbers of labels per protein, would provide immediate feedback on experimental outcomes prior to embarking on detailed LC-MS analyses. To this end, we describe an approach to integrate intact MS screening of labeled samples immediately following exposure, along with metrics to quantify the extent of observed labeling from the intact mass spectra. Intact MS results on the model protein lysozyme were evaluated in the context of Alexa488 assay results and a bottom-up LC-MS analysis of the same samples. In conclusion, this approach provides a basis for placing delivered hydroxyl radical dose metrics on firmer technical grounds for synchrotron X-ray footprinting of proteins, with explicit parameters to increase the likelihood of a productive experimental outcome. Further, the method directs approaches to provide absolute and direct dosimetry for all types of labeling for protein footprinting.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

A high throughput assay to detect enzymatic polyethylene oxidation

Biological plastics deconstruction and upcycling have emerged as sustainable alternatives to traditional recycling technologies for plastics waste. The discovery and engineering of efficient thermostable poly(ethylene terephthalate) (PET) hydrolases have made biological PET recycling possible at scale; however, enzymes for non-PET plastics, which account for approximately 70% of all plastics produced, remain largely undiscovered. To accelerate the discovery of such enzymes, we develop a high-throughput screen to detect initial polymer oxidation, specifically that of the C-H bond to an aldehyde. We test 4-hydrazino-7-nitro-2,1,3-benxoxadiozole hydrazine (NBD-H), which reacts with generated aldehydes to form a fluorescent hydrazone on plasma oxidized low-density polyethylene (LDPE) films. Hydrazone generation correlated well with the area of aldehyde peaks as measured by Fourier Transform Infrared Spectroscopy (FTIR) (R2 = 0.92). Moreover, we demonstrate that the probe reliably identifies LDPE-active dye decolorizing peroxidases (DyPs) that generate aldehydes on LDPE films (1.7 – 3.0 fold change relative to background), serving as an effective screen as demonstrated by receiver operating characteristic area under the curve of 0.95. Furthermore, this assay offers an LDPE oxidation screening platform that can be readily parallelized and automated for accelerated discovery of enzymes involved in polyolefin deconstruction.

biocatalysis↗
DOE OSTI2022

Vapor–liquid equilibrium estimation of n-alkane/nitrogen mixtures using neural networks

Understanding fluid phase behavior, like VLE, in high P&T conditions is crucial for developing high-fidelity simulations of chemically reacting flows in liquid-fueled combustion systems and also forms an integral part of the design-modeling of the control processes in chemical industries. Two data-driven models have been proposed here in this study, each of which was competent in estimating VLE for the Type III binary systems of C 10 /N 2 and C 12 /N 2 , at pressures ranging up to 50–60 MPa. Both models showed better performance in predicting equilibrium pressure as compared to VLE modeled using PR-EOS. A modified model has also been proposed, capable of estimating the full phase envelope for the binary systems of C 10 /N 2 and C 12 /N 2 across a wide range of temperatures, and thus exhibit the mixture critical pressure at the concerned temperature. The diverse applicability of the proposed network architecture was further exhibited while estimating the VLE of a ternary system of C 1 /C 10 /N 2 .

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

O 2 -Oxidation of Individual Graphite and Graphene Nanoparticles in the 1200 – 2200 K Range: Particle-to-Particle Variations and the Evolution of the Reaction Rates and Optical Properties

The kinetics for O 2 oxidation of individual graphite and graphene platelet nanoparticles (NPs) were studied as a function of temperature (1200 to 2200 K) at varying oxygen partial pressures, using a single nanoparticle mass spectrometry method. NP temperature (TNP) was measured by measuring the NP thermal emission spectra during the kinetics studies. The initial oxidation efficiency is found to peak in the 1200 to 1500 K range, dropping by an order of magnitude as TNP was increased above 2000 K. There were large NP-to-NP variations in the oxidation rates, attributed to variations in the NP surface structure. In addition, the oxidation efficiencies evolved, non-monotonically, as the NPs reacted, decreasing by factors of between 10 and 300. This evolution of reactivity is attributed to changes in the NP surface structure due to the combination of oxidation and annealing. In conclusion, the optical properties, including wavelength dependence of the emissivity and the absorption cross section for the 532 nm heating laser, also tended to evolve as the NPs oxidized, but differently for each individual NP, presumably reflecting differences in the initial structures and their evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Isotope effect in formaldehyde steam reforming on Pt/m-ZrO 2 : Insight into chemical promotion by alkalis

Infrared spectroscopy, temperature programmed reaction mass spectrometry (TP-reaction/MS), and catalyst testing were used to investigate alkali promotion of dehydrogenation selectivity during formaldehyde steam reforming (FSR) on Pt/m-ZrO 2 . In a preferred pathway, formaldehyde reacts with water forming hydrogen and formate, followed by forward formate decomposition to CO 2 and H 2 . Alkali-doping of 2 wt% Pt/m-ZrO 2 increases catalyst basicity, which weakens the formate C-H bond promoting formate dehydrogenation / decarboxylation. Promotion by alkali in FSR was observed through a formate nu(CH) band shift to lower wavenumbers in infrared spectroscopy, and through a decrease in the normal isotope effect in switching from H-to D-labeled formalde-hyde in TP-reaction/MS.

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

A comparative study of silver- and palladium-exchanged zeolites in propylene and nitrogen oxide adsorption and desorption for cold-start applications

Here, silver and palladium ion-exchanged BEA zeolites (Si/Al = 12.5) and silver ion-exchanged ZSM-5 zeolites (Si/Al = 15) were studied for their ability to adsorb and desorb propylene and NO under simulated diesel exhaust conditions. The adsorption experiment results demonstrated the excellent ability of bare BEA zeolites to adsorb propylene, but only a small amount of NO. The presence of H 2 O inhibited the adsorption of both C 3 H 6 and NO. Ion-exchanging BEA zeolites with Ag (1.2 and 5.1 wt.% Ag/BEA) attenuated the inhibiting effect of H 2 O on C 3 H 6 adsorption, while NO storage remained inhibited. Adsorption experiments indicated that C 3 H 6 and NO competed with each other for Pd sites with C 3 H 6 showing stronger adsorption compared to NO, whereas Ag sites preferentially adsorbed C 3 H 6 . DRIFTS data indicated the formation of nitrate, formate and acetate species on Ag and Pd, while C 3 H 6 and NO adsorption was also observed on the zeolite hydroxyl groups in the absence of H 2 O. However, the C 3 H 6 and NO adsorption on the zeolite hydroxyl groups was significantly inhibited in the presence of H 2 O. Additionally, nitrosyl, acrolein and carbonate species were formed over 1.0 wt.% Pd/BEA. The effluent analysis during the temperature-programmed desorption in the DRIFTS reactor revealed that adsorbed C 3 H 6 and NO reacted during the release to form oxidation reaction byproducts. The 1.0 wt.% Pd/BEA zeolite showed the greatest oxidation ability during desorption with the majority of stored C 3 H 6 converted to CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗