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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Nitrogen-doped carbon for selective pseudo-metal-free hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran: Importance of trace iron impurity

Heteroatoms-doped carbon materials have recently emerged as effective catalysts for various chemical and electrochemical reactions. The free of metals especially noble metals reduces cost and eliminates issues like sintering or leaching of metals at elevated temperatures in solvents. In this work, selective hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is for the first time achieved over simple nitrogen-doped carbon (N-C) catalysts. Further, at optimal reaction conditions, a 91% yield of DMF is obtained with excellent catalyst stability. Extensive characterization, including extended X-ray absorption fine-structure (EXAFS) and soft X-ray absorption spectroscopy (sXAS), model reactions, basic data science analysis, and DFT calculations suggest that ppm of Fe in particular FeN 3 sites formed in pyrolysis, rather than non-metallic elements, drive key steps such as H 2 activation and deoxygenation of –OH during HMF HDO.

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

Bioinspired oxidation of benzyl alcohol: The role of environment and nuclearity of the catalyst evaluated by multivariate analysis

Inspired by copper-containing enzymes such as galactose oxidase and catechol oxidase, in which distinct coordination environments and nuclearities lead to specific catalytic activities, we summarize here the catalytic properties of dinuclear and mononuclear copper species towards benzyl alcohol oxidation using a multivariate statistical approach. Here, the new dinuclear [Cu 2 (μ-L 1 )(μ-pz)] 2+ (1) is compared against the mononuclear [CuL 2 Cl] (2), where (L 1 ) - and (L 2 ) - are the respective deprotonated forms of 2,6-bis((bis(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol, and 3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzaldehyde and (pz) - is a pyrazolato bridge. Copper(II) perchlorate (CP) is used as control. The catalytic oxidation of benzyl alcohol is pursued, aiming to assess the role of the ligand environment and nuclearity. The multivariate statistical approach allows for the search of optimal catalytic conditions, considering variables such as catalyst load, hydrogen peroxide load, and time. Species 1, 2 and CP promoted selective production of benzaldehyde at different yields, with only negligible amounts of benzoic acid. Under normalized conditions, 2 showed superior catalytic activity. This species is 3.5-fold more active than the monometallic control CP, and points out to the need for an efficient ligand framework. Species 2 is 6-fold more active than the dinuclear 1, and indicates the favored nuclearity for the conversion of alcohols into aldehydes.

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

Laser strengthening of additive manufactured edge seal for vacuum insulated glazing with micro-size glass frit

Sealing of glass edge is a key step in developing cost-effective and durable vacuum insulated glazing for the drive towards net-zero energy buildings. In this study, to achieve a high-strength sealing with scalable and low-cost processing, we investigated a novel sealing method based on additive manufacturing and laser process and reported quantitative analysis of the laser assisted method sealing strength and the requirement of vacuum insulation glazing. Micro-size glass frits in printing ink and a continuous-wave laser curing were employed to allow the formation of a hermetic bonding layer with low thermal budget. Controlling various sealing parameters including laser traveling speed, spot diameter, and laser power, the water seepage and mechanical strength of the resulting glass-to-glass bonding were examined. Through the response surface methodology, we identified the optimized sealing condition where the bonding strength reached 5.68 MPa. A comparation of the bonding strength between thermal sealing method and laser-assisted method has been analyzed as well.

42 ENGINEERING↗
DOE OSTI2024

Investigation on gate oxide reliability under gate bias screening for commercial SiC planar and trench MOSFETs

This paper evaluates the impact of the fast high gate-voltage screening technique on gate oxide reliability of commercial 1.2 kV 4H-SiC power metal-oxide-semiconductor field-effect transistors (MOSFETs) with planar and trench gate structures. The measurements are conducted on packaged devices with the intent that the results will be applicable to wafer-level screening. The threshold voltage (V th ) of SiC MOSFETs is measured before and after various screening treatments and recovery process. In addition, constant-voltage time-dependent dielectric breakdown (TDDB) measurements are performed on SiC MOSFETs to obtain the intrinsic lifetime of gate oxide. The objective of this study is to determine the optimal screening conditions and improve screening efficiency without degradation of gate oxide reliability, such as V th shift and reduced oxide intrinsic lifetime. Due to the differences in the gate oxidation process and structural design of SiC planar and trench MOSFETs, the two types of devices exhibit different oxide reliability in the screening process. The recommended screening conditions obtained in this paper reveal that SiC trench MOSFETs can accept higher screening voltages compared to SiC planar MOSFETs. Hence, it can be concluded that more efficient screening techniques can be adopted for SiC MOSFETs with thicker gate oxide to meet the requirements of industrial applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Rationalizing nitrogen-doped secondary carbon particles for practical lithium-sulfur batteries

Nanostructured carbon host materials are widely used to improve both sulfur utilization rate and reaction kinetics in lithium-sulfur (Li-S) batteries. However, high complexity/cost of materials synthesis and difficulty in processing nano-materials into high-mass-loading electrodes are still significant barriers to the development of low-cost and high-energy Li-S batteries. In this study, we reported a generic and scalable synthesis approach to prepare nitrogen-doped secondary carbon particles. By using nitrogen-containing precursor as an integration reagent, the nanosized Ketjen Black particles were integrated into micron-size secondary ones and nitrogen-doped (NKB) simultaneously through a one-step heat treatment. With NKB as an example material, the effects of particle integration degree on the secondary particles’ structures, pore volume and connectivity, sulfur loading capability, and cell performance were studied and discussed. At an optimal integration condition, the NKB particles had significantly improved particle dimensions with well-maintained high specific surface area and pore volume. Here, contributed by the micron size and high pore volume, the NKB/S were successfully used for high-sulfur-loading cathodes (4–7 mg s /cm -2 ) and were able to deliver a specific capacity of ~1100 mAh g -1 at a low-porosity (50%) and lean-electrolyte conditions (E/S =4 µL/mg -1 ). Feasibility of the materials for practical use was validated through scaling up synthesis (40 g/batch), large-area electrode coating, and practical pouch cell (1.6 Ah) assembly and test.

25 ENERGY STORAGE↗
DOE OSTI2020

Performance of 8 × 8 × 32 and 10 × 10 × 32 mm 3 CdZnTe position-sensitive virtual Frisch-grid detectors for high-energy gamma ray cameras

CdZnTe (CZT) crystals with thicknesses up to 20 mm and diameters up to 75 mm have become available from Redlen Technologies, Inc. for making large-volume gamma-ray detectors. The modified growth and optimized annealing conditions allowed Redlen to minimize the dark current and improve the uniformity of CZT crystals. Two detector designs, pixelated (H3D) and position-sensitive virtual Frisch-grid (VFG), have greatly benefitted from the availability of such big crystals. Encouraging results from testing of 40×40×15 mm 3 pixelated detectors were recently reported by the University of Michigan. In this work, we evaluated the spectroscopic properties of 8×8×32 and 10×10×32 mm 3 crystals configured as position-sensitive VFG detectors. Both digitized waveforms and an analog ASIC were used to read and process the signals from the detectors and test their spectral- and spatial-resolution. The VFG design provides the flexibility to scale-up the dimensions of the detectors for the desired efficiency, while the position information allows for correcting the detectors' response non-uniformity caused by crystal defects and devices geometry, thereby reducing the instrument cost and making them more feasible for emerging applications in gamma-ray astronomy, nonproliferation, portal screening and nuclear safeguards, where large detector arrays are often required.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Integration of a Wigner effect-based energy storage system with an advanced nuclear reactor

In this work, an innovative energy storage concept based on the purposeful creation of defects in crystalline material by neutron irradiation is presented. Lattice defects are generated when heavy particles collide with the atoms in a crystal structure, i.e., if the incoming particles have enough energy, recoil atoms are displaced from their initial lattice sites. Most of the displaced atoms will eventually combine with nearby vacancies, but some of them will come to rest in non-ideal locations. The energy held by displaced atoms is called Wigner energy. Lattice defects can migrate and form clusters, and the Wigner energy can be released from these groupings if sufficient activation energy is provided. In the nuclear industry, this effect is well-known since it represented an issue for graphite-moderated reactors. This work presents the conceptual design of an engineering system that exploits this physical process to store the energy of neutrons in advanced reactor concepts. In the first part of the paper, the theoretical performance of an energy storage system based on the Wigner effect is described. Given the lattice properties and the compatibility with the harsh reactor environment, graphite was selected as the candidate material for the irradiation targets. Both experimental data and molecular dynamics simulations confirmed that this system can achieve performance comparable with state-of-the-art batteries in terms of stored energy density. In the second part of the paper, the engineering challenges of this innovative technology and the proposed solutions are described. After defining the optimal irradiation conditions, the different steps of the operation of the proposed energy system (from energy storing to energy harvesting) were defined. Finally, the integration of this concept with advanced reactor designs, i.e., a Sodium-cooled Fast Reactor and a Molten Salt-cooled Reactor, was investigated and the corresponding performance was evaluated.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2026

A mathematical design framework for membrane pre-concentration in energy-efficient recovery of fermentation products

Due to the dilute nature of products manufactured via fermentation and cell-free bioprocessing, dewatering is a common unit operation in downstream processing (DSP) for bioproduct recovery, but it is typically energy intensive. To improve DSP energy efficiency for bio-based small molecules, integrating high-pressure membrane pre-concentration is a promising process option. However, this approach is typically constrained by a tradeoff between concentration factor (CF) and product recovery (PR), namely increasing the CF typically results in greater product loss, and vice versa. Here we developed a model that enables process design guidelines to: (i) identify scenarios in which the additional energy consumption and product loss from membrane pre-concentration are justified for use in DSP, and (ii) determine the optimal CF that minimizes process specific energy consumption. We compared the energy consumption of high-pressure membrane-integrated processes to evaporation-only processes and applied the model to an experimental case study for the separation and purification of butyric acid from Clostridium tyrobutyricum fermentation using an in situ product recovery (ISPR) process. The model estimated that integrating a tangential-flow reverse osmosis (RO) pre-concentration unit could reduce process energy consumption up to 45%. The use of advanced membrane pre-concentration technologies, such as negative rejection membranes and organic solvent reverse osmosis (OSRO), have the potential to further reduce the overall process specific energy consumption up to 96%, projected based on modeling. Overall, membrane pre-concentration, especially when strategically integrated prior to an evaporation step with optimized process conditions, holds significant potential for improving DSP energy efficiency, particularly in applications requiring substantial solvent removal for product recovery from dilute mixtures.

09 BIOMASS FUELS↗
DOE OSTI2023

Conversion efficiency improvement of ELO GaAs solar cell, deposited on water soluble sacrificial buffer

Here, we demonstrate the improvement of power conversion efficiency of an epitaxially-lifted-off single junction GaAs solar cell deposited on a water-soluble sacrificial buffer architecture by introducing an additional germanium (Ge) interlayer between GaAs and the fluoride buffer. The epitaxial lift-off (ELO) technique has been extensively used to separate III-V device layers from their single crystal GaAs substrates. However, conventional ELO requires the use of concentrated hydrofluoric acid (HF) for extended times to etch out the sacrificial layer, subsequently degrading the surface roughness of the parent wafer. As a result, the wafer has to undergo expensive and intensive chemical mechanical polishing (CMP) processes, costing about 25% of a pristine 6-inch GaAs substrate. In our previous work, we demonstrated a method to eliminating the need for CMP post-processing by using water-assisted ELO (H 2 O-ELO). A water-soluble, 3-layer buffer architecture was developed using alkaline earth compounds. However, devices suffered low performance due to a high defect density in the GaAs active layers. A Ge interlayer was introduced to provide a more favorable surface energy for GaAs growth, which leads to an improvement of GaAs crystal quality. The Ge deposition conditions were optimized to achieve a high-quality Ge layer on triple-layer fluoride buffer. Single junction GaAs devices fabricated on Ge/(Ca,Sr)F 2 /BaF 2 /(Ca,Sr)F 2 showed improvement of solar cell performance parameters featuring increases in V oc by 23.7%, and fill factor (F.F.) by 4.9%, which results in an overall improvement of power conversion efficiency from 10.3% to 12.69%.

14 SOLAR ENERGY↗
DOE OSTI2024

Carbon-sequestration gradient insulation composites

The massive use of carbon-sequestration building materials promises a potential global carbon sink in decarbonizing the building industry. Renewable biogenic materials from abundant agriculture waste for building practice have been around over thousands of years. However, in addition to their flammability and moisture problems, addressing their low thermal and structural performance is also becoming indispensable and urgent when it comes to environmentally sustainable and energy-efficient buildings. Here, we report a nature-inspired biogenic gradient insulation composite with an optimized silica concentration of 30 wt %, a density of 0.246 g/cm 3 , and a porosity of 86%. The gradient hybrid composite exhibits a thermal conductivity of 28.2 mW m -1 K -1 , which is the lowest achieved under optimal preparation conditions. Here, it also shows a flexural modulus of 590 MPa for the aerogel-rich layer without surface modification, and it demonstrates superior fire retardancy and superhydrophobicity after surface treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effect of the Precursor Chemistry on the Crystallization of Triple Cation Mixed Halide Perovskites

Triple cation, mixed halide perovskite compositions have been reported to be more thermally stable, exhibit fewer phase impurities, and show higher power conversion efficiency and better reproducibility than single cation perovskites. In this work, we explain the formation of Cs0.05FA0.81MA0.14Pb(I0.85Br0.15)3 via a multimodal in situ study combining structural information from synchrotron grazing-incidence wide-angle X-ray scattering (GIWAXS) and optical properties from photoluminescence (PL) spectroscopy with density functional theory calculations (DFT). The focus here is on the effects of the solvent and antisolvent during crystallization. The predominantly used solvents N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and the antisolvent chlorobenzene (CB) as well as the solvent-antisolvent-precursor interactions are investigated. Given the high elemental complexity and mutual interdependencies between solvent, antisolvent, and perovskite precursors, we found significant differences in the crystallization pathways. DMF-pure precursors show the formation of the DMF-containing intermediate phase and the nucleation of compositionally distinct perovskite phases, while when DMSO is added, only crystalline α- and δ-phases were found. In addition, the presence of DMSO helps the formation of α-perovskite. Coordination energy and bond order (BO) calculations support our experimental findings. Dripping of CB induces nucleation at room temperature, slows the α-phase formation rate, and appears to reduce the nucleation radius. These findings provide novel insights into solvent, antisolvent, and perovskite precursor interactions and their formation pathways. The complexity of interactions between solvents and reagents highlights the importance of understanding these effects to further improve the reproducibility and optimize processing conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Microfluidic Investigation of Salinity-Induced Oil Recovery in Porous Media during Chemical Flooding

High and low salinity water flooding are common oil recovery processes performed in the oil fields for extracting crude oil from the reservoir. These processes are often performed sequentially, naturally establishing non-uniform salinity in the porous subsurface. In this article, we investigate oil transport in porous media induced by salinity change upon flooding with high and low salinity water. As we observe a large number of impervious dead-ends from three-dimensional imaging of the actual reservoir, we identify that these areas play an important role in oil recovery where the oil transport is governed by the salinity change rather than hydrodynamics. The salinity gradients induced upon high salinity water flooding provide pathways to enhance the transport of oil drops trapped in the dead-end regions via non-equilibrium effects. However, above a critical salinity, we observe a rapid aggregation of drops that lead to the complete blockage of the pore space, thereby inhibiting oil recovery. We also find that, at an intermediate salinity where the drop aggregation is modest, the aggregation rather promotes the oil recovery. Furthermore, our observations suggest that there exist optimal salinity conditions for maximizing oil recovery during chemical flooding.

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

Defluorination Mechanisms and Real-Time Dynamics of Per- and Polyfluoroalkyl Substances on Electrified Surfaces

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants found in groundwater sources and a wide variety of consumer products. In recent years, electrochemical approaches for the degradation of these harmful contaminants have garnered a significant amount of attention due to their efficiency and chemical-free modular nature. However, these electrochemical processes occur in open, highly non-equilibrium systems, and a detailed understanding of PFAS degradation mechanisms in these promising technologies is still in its infancy. To shed mechanistic insight into these complex processes, we present the first constant-electrode potential (CEP) quantum calculations of PFAS degradation on electrified surfaces. These advanced CEP calculations provide new mechanistic details about the intricate electronic processes that occur during PFAS degradation in the presence of an electrochemical bias, which cannot be gleaned from conventional density functional theory calculations. We complement our CEP calculations with large-scale ab initio molecular dynamics simulations in the presence of an electrochemical bias to provide time scales for PFAS degradation on electrified surfaces. Taken together, our CEP-based quantum calculations provide critical reaction mechanisms for PFAS degradation in open electrochemical systems, which can be used to prescreen candidate material surfaces and optimal electrochemical conditions for remediating PFAS and other environmental contaminants.

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

Technoeconomic Analysis of the Electrochemically Mediated Amine Regeneration CO 2 Capture Process

The electrochemically mediated amine regeneration (EMAR) process presents an alternative route to the conventional thermal amine regeneration for carbon capture from a flue gas source. In this study, we conducted an economic analysis on the EMAR system for postcombustion CO2 capture from a 550 MWe power plant capturing 3.1 MtCO2 annually and from a mini steel mill with annual capture close to 170 ktCO2. We followed the recommendation of the National Energy Technology Laboratory (NETL) 2010 report to estimate the cost of CO2 avoided ([$/tCO2]). Detailed cost modeling of the electrochemical separation stage was conducted. This is integrated with the entire process flowsheet (e.g., including absorber, compressor, pumps, and other auxiliary equipment). Here, we identified the membrane cost as the dominant capital cost for the electrochemical separation train. At a membrane unit price of less than 10/m2, the CO2 capture cost can be reduced to below 50/tCO2 with optimized process conditions (e.g., desorption pressure and utilization of waste heat). Improvements in process design, cell construction, and solvent formulation may lead to additional reductions in the CO2 capture cost.

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

A Comparative Study of Electrical Double Layer Effects for CO Reduction Reaction Kinetics

Solvation models describe how the interactions between the solutes and solvents affect the reactivity and selectivity in electrochemical processes. In this study, we developed a framework for evaluating the effects of applied potential and electrical double layer on CO reduction (COR), comparing fully explicit, implicit, and hybrid solvation models at the standard hydrogen electrode (SHE) scale. We analyzed all crucial intermediates leading to the production of C 1 and C 2 products and found good agreement across these models. Some notable differences were observed in the implicit description of *C and *CO adsorption at higher overpotentials and overall trends in the adsorption energies within the hybrid model. Using this unified SHE framework, we built comparable microkinetic models for COR kinetics and rates. Despite small differences in thermodynamics, solvation-model-based microkinetic simulations showed good agreement for onset potentials against the benchmark experiment. Only qualitative difference was observed for C 1+ versus hydrogen evolution at high overpotentials for the implicit model. Finally, we constructed a generalized C 2 selectivity map in descriptor space (U SHE , ΔG electrolyte CO ), which highlights the limitations of a copper-based COR catalyst and guides the search for optimal descriptor parameters to maximize C 2 selectivity. In conclusion, these findings demonstrate the importance of considering electrical double layer effects in reduction reactions and offer a useful framework for comparing solvation models and predicting optimal electrochemical conditions for specific applications.

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

Resonance-Promoted Formic Acid Oxidation via Dynamic Electrocatalytic Modulation

It is a truth universally acknowledged that faster catalysts enable more efficient transformation of molecules to useful products and enhance the utilization of natural resources. However, the limit of static catalyst performance defined by the Sabatier principle has motivated a dynamic approach to catalyst design, whereby catalysts oscillate between varying energetic states. In this work, the concept of dynamic catalytic resonance was experimentally demonstrated via the electrocatalytic oxidation of formic acid over Pt. Oscillation of the electrodynamic potential between 0 and 0.8 V NHE via a square waveform at varying frequency (10 –3 < f < 10 3 Hz) increased the turnover frequency to ~20 s –1 at 100 Hz, over one order of magnitude (20×) faster than optimal potentiostatic conditions. We attribute the accelerated dynamic catalysis to nonfaradaic formic acid dehydration to surface-bound carbon monoxide at low potentials, followed by surface oxidation and desorption to carbon dioxide at high potentials.

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

Data-Driven Discovery of Bimetallic Nanoparticles Catalysts for the Hydrogenolysis of Polyethylene

Supported platinum nanoparticles are known to convert polyolefins to high-quality liquid hydrocarbons with hydrogen under relatively mild conditions. However, no systematic study has been undertaken using bimetallic catalysts for polyethylene upcycling. Specifically, a total of 98 monometallic and bimetallic combinations (Ag, Cr, Co, Cu, Fe, Ga, In, Mn, Ni, Pd, Pt, Rh, Ru, Zr) on alumina were synthesized utilizing surface organometallic chemistry (SOMC) technique via robotic platform. These were investigated at a small scale (10 mg of catalyst and 50 mg of polyethylene) for their activity for the hydrogenolysis of polyethylene in a high-throughput batch reactor. Combinations of Ni and Co were selected as candidates with high activity toward conversion into paraffin oils. Reaction conditions were optimized with Ni/Co/Al 2 O 3 catalyst at a larger scale (300 mg catalyst and 3 g polyethylene) to obtain a high yield (93.1%) of paraffin wax with desired properties (M n = 380 Da) and low polydispersity (Đ = 1.2). Ni/Co/Al 2 O 3 was compared against Co/Ni/Al 2 O 3 to understand the role of the deposition sequence. When Co is deposited before Ni, a layer of cobalt aluminate is formed upon reduction, stabilizing the deposition of 5 nm metallic Ni particles. When nickel is deposited before Co, particles are larger (average >20 nm) and more oxidized (Ni δ+ in NiAl 2 O 4 ), decreasing the availability of the catalytically active metallic Ni. In conclusion, the difference in electronic environments was also described by DFT calculations, which revealed that smaller 3D clusters of Ni are preferred on CoAl2O4 over the 3D clusters on NiAl 2 O 4 and that these smaller clusters are more reducible, as confirmed experimentally.

Polymer↗