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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Assembly of Building Blocks by Double-End-Anchored Polymers in the Dilute Regime Mediated by Hydrophobic Interactions at Controlled Distances

Hierarchical assembly of building blocks via competing, orthogonal interactions is a hallmark of many of nature’s composite materials that do not require highly specific ligand-receptor interactions. To mimic this assembly mechanism requires the development of building blocks capable of tunable interactions. In the present work, we explored the interplay between repulsive (steric and electrostatic) and attractive hydrophobic forces. The designed building blocks allow hydrophobic forces to effectively act at controlled, large distances, to create and tune the assembly of membrane-based building blocks under dilute conditions and affect their interactions with cellular membranes via physical cross-bridges. Specifically, we employed double-end-anchored poly(ethylene glycol)s (DEA-PEGs)—hydrophilic PEG tethers with hydrophobic tails on both ends. Using differential-interference-contrast optical microscopy, synchrotron small angle X-ray scattering (SAXS), and cryogenic electron microscopy, we investigated the ability of DEA-PEGs to mediate assembly in the dilute regime on multiple length scales and on practical time scales. The PEG length, anchor hydrophobicity, and molar fraction of DEA-PEG molecules within a membrane strongly affect the assembly properties. Additional tuning of the intermembrane interactions can be achieved by adding repulsive interactions via PEG-lipids (steric) or cationic lipids to the DEA-PEG-mediated attractions. Further, while the optical and electron microscope imaging methods provided qualitative evidence of the ability of DEA-PEGs to assemble liposomes, the SAXS measurements and quantitative line-shape analysis in dilute preparations demonstrated that the ensemble average of loosely organized liposomal assemblies maintains DEA-PEG concentration-dependent tethering on defined nanometer length scales. For cationic liposome–DNA nanoparticles (CL–DNA NPs), aggregation induced by DEA-PEGs decreased internalization of NPs by cells, but tuning the DEA-PEG-induced attractions by adding repulsive steric interactions via PEG-lipids limited aggregation and increased NP uptake. However, confocal microscopy imaging together with colocalization studies with Rab11 and LysoTracker as markers of intracellular pathways showed that modifying CL–DNA NPs with DEA-PEGs alters their interactions with the plasma and endosomal membranes.

- x-ray scattering↗
DOE OSTI2023

Design Criteria of Dilute Ether Electrolytes toward Reversible and Fast Intercalation Chemistry of Graphite Anode in Li-Ion Batteries

To date, dilute ether electrolytes have been believed to be incompatible with graphite in Li-ion batteries due to the detrimental solvent cointercalation and graphite exfoliation. Here, in this paper, we provide design criteria of dilute ether electrolytes for a reversible graphite anode based on tailoring the solvation structures and thermodynamic properties. We clarify that ether solvents can support graphite reversibly by modulating the anion. Our redesigned electrolyte consisting of a single-solvent 1,3-dioxolane (DOL) and 1 M single-salt lithium bis(fluorosulfonyl)imide (LiFSI) shows weakened Li-solvent interaction and results in an inorganic-rich solid-electrolyte interphase. Consequently, we achieved ~99.9% Coulombic efficiency with >96% capacity retention (~350 mAh/g) after 300 cycles at C/5 using natural graphite. The weakly solvated electrolyte maintains desirable transport properties, enabling better rate capability than carbonate electrolytes with an areal capacity of 2–4 mAh/cm 2 . We have demonstrated the potential of dilute ether electrolytes for facile desolvation-based intercalation chemistry in graphite, creating a viable path toward fast-charge Li batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Directional clogging and phase separation for disk flow through periodic and diluted obstacle arrays

We model collective disk flow though a square array of obstacles as the flow direction is changed relative to the symmetry directions of the array. At lower disk densities there is no clogging for any driving direction, but as the disk density increases, the average disk velocity decreases and develops a drive angle dependence. For certain driving angles, the flow is reduced or drops to zero when the system forms a heterogeneous clogged state consisting of high density clogged regions coexisting with empty regions. The clogged states are fragile and can be unclogged by changing the driving angle. For large obstacle sizes, we find a uniform clogged state that is distinct from the collective clogging regime. Within the clogged phases, depinning transitions can occur as a function of increasing driving force, with intermittent motion appearing just above the depinning threshold. The clogging is robust against the random removal or dilution of the obstacle sites, and the disks are able to form system-spanning clogged clusters even under increasing dilution. If the dilution becomes too large, however, the clogging behavior is lost.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Additive manufacturing of high explosives with inert dilution for wave shaping and detonation velocity grading

The performance of a high explosive charge is highly influenced by the detonation velocity and any inherent internal structure. Additively manufactured (AM) high explosive charges allow for a precisely engineered internal structure and the selective placement of discrete or graded volumes of a tailored material, which are unachievable by conventional means. The dilution of a solid explosive by an inert additive for detonation velocity reduction is herein evaluated for a method of material extrusion called a direct-ink-write AM, where an 1,3,5,7-tetranitro-1,3,5,7-tetrazoctane-based ultraviolet -curable energetic-binder paste explosive was diluted by the inert density mock 5-iodo-2′-deoxyuridine for use in the manufacture of multi-material explosive charges. The explosive ink was characterized for printing by rheological and particle size measurements, and the detonation velocities for 0–40 wt. % inert diluent were found to have a continuous linear reduction in detonation velocity down to 14.3% difference. A two-component 3D plane wave explosive lens with 8.038 km/s “fast” and 7.491 km/s “slow” diluted ink in an internal cone demonstrated a reduced time of breakout at the output face from 361 to 53 ns. A linearly graded “fast–slow–fast” cylinder was successfully printed and fired, showing engineered control along the length of the charge as the detonation velocity dropped from 7.851 to 6.700 km/s and then recovered to 7.241 km/s. The extreme control over the internal composition of a high explosive charge via a dual-material extruder/mixer challenges conventional manufacturing approaches and opens new avenues for engineered detonation wavefronts, high explosive charge performance, and new applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Influence of heterovalent doping on tetrahedral N interstitial formation in dilute GaAsN alloys

Dilute alloying of GaAs with N enables bandgap tuning for near-infrared to mid-infrared optoelectronic devices. However, non-substitutional N incorporation has been linked to lower absorption and emission efficiencies in dilute-nitride-alloy-based devices, especially in those containing heterovalent dopants. Here, in this work, we examine the influence of heterovalent dopants on N incorporation mechanisms in dilute GaAs 1−x N x alloys with N composition intentionally below the threshold composition for the formation of tetrahedral N interstitials (N tetra ) in undoped GaAs 1−x N x . For undoped GaAs 1−x N x , 20% of the N incorporates in non-substitutional sites, as (N-N) As and (N-As) split interstitials. Interestingly, Si dopants induce the formation of N tetra , while Be doping has a negligible effect on the interstitial type. Although elastic interactions due to opposite signs of the misfit volumes of N tetra and N As contribute to N tetra incorporation above a threshold N composition, Si dopants reduce the threshold composition, due to the Fermi level-dependent stability of N tetra .

36 MATERIALS SCIENCE↗
DOE OSTI2025

Loading Capacity and Dilute Nitric Acid Rinse of Diglycolamide Resin for the Recovery of Transplutonium and Rare Earth Elements from Mark-18A Targets

N,N,N′,N′-tetraoctyldiglycolamide (TODGA) as a resin (“DGA resin”) produced by Eichrom Technologies will be used by Savannah River National Laboratory for the indiscriminate extraction of trivalent actinides and rare earth elements with the intent of recovering Cm and Am from dissolved irradiated 242 Pu Mark-18A targets in 7 to 9 M nitric acid. The extracted constituents will be recovered as an oxide by direct thermal decomposition of the loaded resin followed by calcination of the resultant residue. The characteristics of DGA resin with non-radiological feed simulant representative of the anticipated feed in the Mark-18A process, with Sm and Nd as surrogates for Cm and Am, respectively, including breakthrough point and saturation capacity were evaluated in this work. Additionally, this work examined the losses from the loaded resin by rinsing the resin bed with dilute acid to reduce the nitrate concentration in the resin bed prior to thermal decomposition operations to improve the safety posture of the process. A resin loading profile was developed, and the resin was determined to have a trivalent metal saturation capacity of 74 μmol/mL resin under the experimental conditions evaluated. Following a wash of the loaded resin bed with fresh 8 M HNO 3 , the trivalent metals retained was reduced to 68 μmol/mL resin, which represents the practical capacity of the resin for the Mark-18A process. Lighter lanthanides breakthrough the resin well before the saturation capacity is reached. Rinsing the saturated resin bed with 0.26 M HNO 3 was found to result in a rapid reduction in retention of rare earth elements by the resin. After 2.8 bed volumes of dilute acid rinse, the mean resin bed free acid concentration was reduced to 0.28 M and 3.1 bed volumes of dilute acid rinse resulted in a reduction of the cumulative rare earth element retention to 52 μmol/mL of resin.

Transplutonium separations↗
DOE OSTI2020

Dynamical resilience to disorder: The dilute Hubbard model on the Lieb lattice

In itinerant systems, electron-electron interactions may lead to the formation of local magnetic moments and their effective exchange coupling, which in turn gives rise to long-range magnetic order. Therefore, when moment formation is weakened, such as in the single-band Hubbard model on a square lattice with the on-site repulsion being randomly switched off on a fraction $\textit{x}$ of sites, magnetic order is suppressed beyond some critical $x_c$, which was found to lie below the classical percolation threshold $x^{\text{(perc,sq)}}_c$. Here we study dilute magnetism in flat band systems, namely, in the Hubbard model on a “Lieb” lattice. Interestingly, we show that magnetic order persists to x almost twice as large as the classical percolation threshold for the lattice, thus emphasizing the central role of electron itinerancy to the magnetic response. Further, the analysis of the orbital-resolved order parameters reveals that the contribution of the fourfold coordinated $\textit{“d”}$ sites to magnetism is dramatically affected by dilution, while the localized $\textit{“p”}$ states of the flat band provide the dominant contribution to long-range correlations. We also examine the transport properties, which suggest the existence of an insulator-to-metal transition in the same range of the critical magnetic dilution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Anomalous frequency and temperature dependent scattering in the dilute metallic phase in lightly doped-SrTiO 3

The mechanism of superconductivity in materials with aborted ferroelectricity and its emergence out of a dilute metallic phase in systems like doped-SrTiO 3 is an outstanding issue in condensed matter physics. This dilute metal has anomalous properties that are both similar and different to those found in the normal state of other unconventional superconductors. For instance, T 2 resistivity can be found at densities that are too small to allow current decay through electronelectron scattering. We have investigated the optical properties of the dilute metallic phase in doped-SrTiO 3 using THz time-domain spectroscopy. At low frequencies the THz response exhibits a Drude-like form as expected for typical metal-like conductivity. We observed the frequency and temperature dependencies to the low energy scattering rate Γ(ω, T) ∝ (¯hω) 2 + (pπk B T) 2 expected in a conventional Fermi liquid. However we find the lowest known p values of 0.39-0.72. As p is 2 in a canonical Fermi liquid and existing models based on energy dependent elastic scattering bound p from below to 1, our observation lies outside current explanation. Our data also gives insight into the high temperature regime and shows that the temperature dependence of the resistivity derives in part from strong T dependent mass renormalizations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Next-Cycle Optimal Dilute Combustion Control via Online Learning of Cycle-to-Cycle Variability Using Kernel Density Estimators

Dilute combustion using exhaust gas recirculation (EGR) presents a cost-effective method for increasing the efficiency of spark-ignition (SI) engines. However, the maximum amount of EGR that can be used at a given condition is limited by a rapid increment of cycle-to-cycle variability (CCV). This study describes a methodology to design a model-based stochastic optimal controller to adjust the cycle-to-cycle fuel injection quantity in order to reduce CCV and further extend the dilute limit. Given the complexity and chaotic nature of combustion events, the controller was enhanced with online learning in order to identify the statistical properties of combustion efficiency, which are needed to generate predictions for next-cycle events. This study showed that a kernel density estimator (KDE) can be used to learn the combustion properties in real time and can be incorporated into the feedback policy in order to calculate the optimal control command. Experimental results suggested that the dilute limit can be extended from 18.5% to 21% EGR fraction at an operating condition relevant for highway cruising. Additionally, the proposed controller can achieve a large CCV reduction with less fuel enrichment compared to previous methods, overall contributing to an increase in 0.2% indicated fuel conversion efficiency.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2025

Entrainment, Detrainment, and Dilution of Dry and Moist Atmospheric Thermals

Here this study examines the entrainment, detrainment, and dilution of dry and moist (cloud) atmospheric thermals in large-eddy simulations. In a neutrally stable environment (with respect to dry dynamics), moist thermals have an increase in radius R with thermal height z t (α ≡ dR/dz t ) about 4 times smaller compared to dry thermals when density stratification is considered and ~2.4 times smaller without density stratification (i.e., applying the Boussinesq approximation). An analytic expression relating α to several dimensionless parameters is derived from the thermal impulse–circulation relation to clarify the factors impacting α. This expression shows that the difference in buoyancy structure between moist and dry thermals, with buoyancy concentrated in the central cores of moist thermals owing to latent heating, explains their smaller spreading rates. Individual contributions of entrainment and detrainment are analyzed using a direct parcel-based approach in the simulations. Moist thermals have similar fractional detrainment but much smaller fractional entrainment rates compared to dry thermals, consistent with the differences in α. Despite having smaller α, moist thermals are similarly dilute (quantified by a passive tracer) as dry thermals because of their greater mixing efficiency with the environment. Thus, moist thermals are substantially dilute but expand much less in size/volume as they rise compared to dry thermals. The α values for moist thermals in (dry) neutral and statically stable environments are similar, but fractional entrainment and especially detrainment rates are greater in the stable environment. Large detrainment rates are associated with a breakdown of the broader thermal vortex ring structure, especially with low environmental relative humidity, attributed in part to evaporation and buoyancy reversal.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

System Integration of Rationally Designed Dilute Alloy Catalysts for Energy-Efficient Electrochemical CO 2 -To-Fuel Conversion

Energy effiecient electrochemical conversion of CO 2 to high-demand chemicals and transportation fuels using renewable solar and wind energy is a key technology needed for a high-productivity, low-carbon future. However, the development of scalable, low-cost, active, selective, and stable electrocatalysts remains a key challenge that needs to be overcome to enable high-volume conversion of CO 2 to feedstock chemicals for the chemical industry. In previous work, Lawrence Livermore National Laboratory (LLNL) has developed a rational design platform for dilute alloy transition metal electrocatalysts that promise to make electrochemical CO 2 conversion more energy efficient and selective. In this project, we worked with our industrial partners, Twelve and TotalEnergies, to improve scale up, integration, and stability of LLNL’s dilute alloy catalyst technology into an industry-relevant zero gap electrolyzer platform. Through virtual experiments and data analysis, we designed efficient and cost-effective copper-based catalysts. The catalyst was specifically designed to streamline the slowest and most energy-intensive step of the electrochemical chemical transformation of CO 2 to multi-carbon products – that is making the carbon-carbon bond by dimerization of the reaction intermediate carbon monoxide - resulting in up to 10% improvement in energy efficiency for C 2 products while simultaneously increasing the selectivity towards C 2 products. We tested two different scalable catalyst coating technologies and down-selected magnetron sputtering as the technique that provided the best control over catalyst loading, composition, and morphology. Using this technology, we successfully demonstrated integration of our dilute alloy catalysts into a 100 cm 2 electrolyzer platform with Faradaic efficiencies for ethylene production reaching 40% at a current density of 200 mA/cm 2 . We also developed the technology to integrate a well-defined nanoscale porosity by depositing alloy compositions that were compatible with dealloying, that is, selective leaching of an alloy component to generate nanoscale porosity. We observed that integration of the dealloying-derived nanoporosity improved catalyst performance and stability by leading to a more hydrophobic catalyst/anion exchange membrane interface. Unsolved problems that still need to be addressed are corrosion of the Cu catalyst -specifically if the used catalyst is exposed to air - as well as long term stability do to salt formation/deposition and flooding of the catalyst/electrolyzer flow channels, especially at higher current densities. As we only worked on optimization of catalyst composition, coating thickness, and morphology, further performance optimization will require a system level approach that includes optimization of electrolyzer design and membrane technology.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Cryocooled cold trap system for the SuperCDMS dilution refrigerator

Operating 6,800 feet underground at the SNOLAB facility in Sudbury, Ontario, Canada, the dilution refrigerator-cooled SuperCDMS SNOLAB (Super Cryogenic Dark Matter Search at the Sudbury Neutrino Observatory Laboratory) experiment has been designed for maximum cryogenic up-time and remote operations. A key element in achieving these goals is a pair cold traps in the helium circulation stream of the dilution refrigerator; the first operating near liquid nitrogen temperatures and the second operating near liquid helium temperatures. Previous experience with the CDMS experiment, located underground at the Soudan Under-ground Laboratory, has given significant operational experience with dilution refrigerator cold traps and has solidified the demand of a system of dual cold traps. Unlike the CDMS-era system, the new SuperCDMS system will feature a cryocooler powered liquid nitrogen re-liquefying system (as opposed to regular under-ground re-filling of cold trap dewars using portable nitrogen dewars) and a cryogen-free 4 K cold trap, which eliminates the need for a bath of liquid helium.

43 PARTICLE ACCELERATORS↗
DOE OSTI2022

D 3 -creatine dilution for skeletal muscle mass measurement: historical development and current status

The French chemist Michel Eugène Chevreul discovered creatine in meat two centuries ago. Extensive biochemical and physiological studies of this organic molecule followed with confirmation that creatine is found within the cytoplasm and mitochondria of human skeletal muscles. Two groups of investigators exploited these relationships five decades ago by first estimating the creatine pool size in vivo with 14 C and 15 N labelled isotopes. Skeletal muscle mass (kg) was then calculated by dividing the creatine pool size (g) by muscle creatine concentration (g/kg) measured on a single muscle biopsy or estimated from the literature. This approach for quantifying skeletal muscle mass is generating renewed interest with the recent introduction of a practical stable isotope (creatine-(methyl-d 3 )) dilution method for estimating the creatine pool size across the full human lifespan. The need for a muscle biopsy has been eliminated by assuming a constant value for whole-body skeletal muscle creatine concentration of 4.3 g/kg wet weight. The current single compartment model of estimating creatine pool size and skeletal muscle mass rests on four main assumptions: tracer absorption is complete; tracer is all retained; tracer is distributed solely in skeletal muscle; and skeletal muscle creatine concentration is known and constant. Three of these assumptions are false to varying degrees. Not all tracer is retained with urinary isotope losses ranging from 0% to 9%; an empirical equation requiring further validation is used to correct for spillage. Not all tracer is distributed in skeletal muscle with non-muscle creatine sources ranging from 2% to 10% with a definitive value lacking. Lastly, skeletal muscle creatine concentration is not constant and varies between muscles (e.g. 3.89–4.62 g/kg), with diets (e.g. vegetarian and omnivore), across age groups (e.g. middle-age, ~4.5 g/kg; old-age, 4.0 g/kg), activity levels (e.g. athletes, ~5 g/kg) and in disease states (e.g. muscular dystrophies, <3 g/kg). Some of the variability in skeletal muscle creatine concentrations can be attributed to heterogeneity in the proportions of wet skeletal muscle as myofibres, connective tissues, and fat. These observations raise serious concerns regarding the accuracy of the deuterated-creatine dilution method for estimating total body skeletal muscle mass as now defined by cadaver analyses of whole wet tissues and in vivo approaches such as magnetic resonance imaging. A new framework is needed in thinking about how this potentially valuable method for measuring the creatine pool size in vivo can be used in the future to study skeletal muscle biology in health and disease.

body composition↗
DOE OSTI2026

Salt mass determination by 22 Na-based radioactive tracer dilution of a highly radioactive molten salt system for pyroprocessing spent oxide nuclear fuels

To demonstrate the feasibility of the 22 Na-based radioactive tracer dilution (RTD) for determining the total salt mass in a 60-kg oxide reduction (OR) system at Idaho National Laboratory (INL) for pyroprocessing spent oxide nuclear fuels, a LiCl- 22 NaCl tracer salt was prepared and spiked to the OR vessel, and salt samples were analyzed by gamma spectroscopy. Due to the high radioactivity (around 10 mCi/g) of the OR salt, mainly from 137 Cs, traditional gamma spectroscopy methods, which typically involve diluted salt samples, was not effective for analyzing the RTD samples. Since the 22 Na tracer radioactivity was very low, undiluted samples were necessary to detect the small amount of 22 Na tracer. Here, despite the high gamma radioactivity of the OR salt, increasing the detector-sample distance from 20 cm to 40 cm during gamma spectroscopy allowed the detection of radioactivity as low as 0.12 µCi/g 22 Na. The preparation of the 22 NaCl-LiCl tracer salt suitable for spiking into the OR salt was successful, and the mass determined by RTD was consistent with that estimated by salt level measurement. Therefore, the 22 Na-based RTD technique for total mass determination of the 60-kg molten salt system for OR is feasible, though more development work, particularly in the improving the uncertainty, is needed .

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
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 OSTI2023

Extraordinary Magnetic Response of an Anisotropic 2D Antiferromagnet via Site Dilution

A prominent characteristic of 2D magnetic systems is the enhanced spin fluctuations, which reduce the ordering temperature. We report that a magnetic field of only 1000th of the Heisenberg superexchange interaction can induce a crossover, which for practical purposes is the effective ordering transition, at temperatures about 6 times the Néel transition in a site-diluted two-dimensional anisotropic quantum antiferromagnet. Such a strong magnetic response is enabled because the system directly enters the antiferromagnetically ordered state from the isotropic disordered state, skipping the intermediate anisotropic stage. The underlying mechanism is achieved on a pseudospin-half square lattice realized in the [(SrIrO3)1/(SrTiO3)2] superlattice thin film that is designed to linearly couple the staggered magnetization to external magnetic fields by virtue of the rotational symmetry-preserving Dzyaloshinskii–Moriya interaction. Furthermore, our model analysis shows that the skipping of the anisotropic regime despite finite anisotropy is due to the enhanced isotropic fluctuations under moderate dilution.

2D antiferromagnet↗
DOE OSTI2022

Hydrogen Dissociation Controls 1-Hexyne Selective Hydrogenation on Dilute Pd-in-Au Catalysts

Increasing the selectivity of the catalytic hydrogenation of alkynes to alkenes is of major importance for the processing of petrochemicals and the production of fine chemicals. Achieving high selectivity for alkene formation at high conversions, however, remains a long-standing challenge in heterogeneous catalysis. Here, the mechanism and origin of the high selectivity of dilute Pd-in-Au catalysts has been studied by a combination of first-principles calculations, microkinetic simulations, and isotopic exchange hydrogenation experiments using Pd 0.04 Au 0.96 nanoparticles embedded in raspberry colloid-templated silica. The Pd is predominantly in the form of isolated atoms, only surrounded by Au atoms, based on prior studies. The simulations indicate that the rate-limiting process for 1-hexyne hydrogenation on Pd monomers in Au(111) is H 2 dissociation, which has a large free energy barrier of 0.86 eV at 363 K and 0.2 bar of H 2 . The C–H bond formation steps, on the other hand, proceed with lower barriers, which contrasts with previous studies of extended Pd catalysts. The microkinetic simulations identify the sizable H 2 dissociation barrier and the small barrier for the hydrogenation of 1-hexyne as key factors that lead to a high selectivity for the production of 1-hexene from 1-hexyne, even at high conversion. The unconventional H 2 dissociation limiting process in combination with the low coverage of weakly bound hydrocarbon intermediates explains the near-zero order of 1-hexyne found experimentally. Furthermore, the partial hydrogenation of 1-hexyne to form 1-hexene is shown to be an irreversible process from our isotopic exchange hydrogenation experiments and is explained by the strongly exothermic nature of the reaction. Diluting active species, like Pd, in a less active host metal, like Au, hence appears promising as a means of tuning the binding energy of reactants and altering reaction profiles, leading to distinct kinetic behavior for an optimal catalytic activity and selectivity. Furthermore, the combination of microkinetic modeling, density functional theory calculations, and isotopic exchange experiments is thus demonstrated to be an effective approach to modeling important catalytic phenomena.

1-hexyne↗
DOE OSTI2020

Cyclic dynamics of misfires and partial burns in a dilute spark-ignition engine

Here, this study investigates the cyclic dynamics of cumulative heat release data past the edge of stability in a dilute spark-ignition engine. Emphasis is placed on analyzing the cyclic dynamics near the dilute limit where partial burns and misfires are frequent. These events are often followed by a higher-energy cycle due to the feed-forward mechanism present in the residual gases. These patterns are deterministic and increase the coefficient of variation to undesirable levels. Symbol sequence analysis was used to investigate the cyclic dynamics of these low–high patterns. The heat release was partitioned on an energy basis to give physical meaning to each partition and each sequence created when analyzing the symbol sequence results. This partitioning method provided insight into the differences in the dynamics when operating in the misfire or partial burn regime. These differences could impact the control method used.

42 ENGINEERING↗