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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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Cyclotrimerization of Acetylene in Gas Phase V + (C 2 H 2 ) n Complexes: Detection of Intermediates and Products with Infrared Spectroscopy

Infrared laser spectroscopy and mass spectrometry were used to determine the structures of intermediates and products in the single-atom-catalyzed trimerization of acetylene to form benzene. Complexes of the form V + (C 2 H 2 ) n were produced in the gas phase via laser ablation in a pulsed-nozzle source, size-selected with a mass spectrometer, and studied with infrared laser photodissociation spectroscopy. Density Functional Theory (DFT) calculations were performed in support of the experiments. Single- and doub le-acetylene complexes form V + (C 2 H 2 ) n metallacycle structures. Three-acetylene complexes exhibit a surprising dependence on the acetylene concentration, forming V + (C 2 H 2 ) 3 and (C 2 H 2 )V + (C 4 H 4 ) tri- and dimetallacycle ion structures at low concentration, and eventually V + (benzene) at higher concentrations. Finally, these observations reveal intermediates along the reaction path of acetylene cyclotrimerization to benzene.

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

Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production

The control of morphology in bioinspired chromophore assemblies is key to the rational design of functional materials for light harvesting. Here, we investigate here morphological changes in perylene monoimide chromophore assemblies during thermal annealing in aqueous environments of high ionic strength to screen electrostatic repulsion. We found that annealing under these conditions leads to the growth of extra-large ribbon-shaped crystalline supramolecular polymers of widths from about 100 nm to several micrometers and lengths from 1 to 10 μm while still maintaining a unimolecular thickness. This growth process was monitored by variable-temperature absorbance spectroscopy, synchrotron X-ray scattering, and confocal microscopy. The extra-large single-crystal-like supramolecular polymers are highly porogenic, thus creating loosely packed hydrogel scaffolds that showed greatly enhanced photocatalytic hydrogen production with turnover numbers as high as 13 500 over ~110 h compared to 7500 when smaller polymers are used. Our results indicate great functional opportunities in thermally and pathway-controlled supramolecular polymerization.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Selective and Efficient Production of Biomass-Derived Vinylfurans

We describe a two-step catalytic process for the selective and rapid conversion of biomass-derived acetylfurans into vinylfurans. This is accomplished by nearly quantitatively reducing acetylfurans into furyl alcohols using a copper chromite catalyst and exploiting the promoter-like properties of ethanol, the solvent. Subsequently, furyl alcohol is dehydrated using solid-acid catalysts. Catalyst deactivation due to oligomeric species is a major issue, but the activity can be partially recovered by calcination. Optimization of reaction conditions showed that the selectivity could be increased by using nitrobenzene, a polar aprotic solvent. Here, the high-boiling point solvent allows the formation of vinylfurans with a selectivity of up to 85%; the product can be isolated in high purity by distillation.

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

Origin of Selective Production of Hydrogen Peroxide by Electrochemical Oxygen Reduction

Oxygen reduction reaction (ORR) is one of the most important electrochemical reactions. Starting from a common reaction intermediate *–O–OH, the ORR splits into two pathways, either producing hydrogen peroxide (H 2 O 2 ) by breaking the *–O bond or leading to water formation by breaking the O–OH bond. However, it is puzzling why many catalysts, despite the strong thermodynamic preference for the O–OH breaking, exhibit high selectivity for hydrogen peroxide. Moreover, the selectivity is dependent on the potential and pH, which remain not understood. Here, for this work, we develop an advanced first-principles model for effective calculation of the electrochemical reaction kinetics at the solid–water interface, which were not accessible by conventional models. Using this model to study representative catalysts for H 2 O 2 production, we find that breaking the O–OH bond can have a higher energy barrier than breaking *–O, due to the rigidity of the O–OH bond. Importantly, we reveal that the selectivity dependence on potential and pH is rooted into the proton affinity to the former/later O in *–O–OH. For single cobalt atom catalyst, decreasing potential promotes proton adsorption to the former O, thereby increasing the H 2 O 2 selectivity. In contrast, for the carbon catalyst, the proton prefers the latter O, resulting in a lower H 2 O 2 selectivity in acid condition. These findings explain the experiments and highlight the kinetic origins of the selectivity. Our work improves the understanding of ORR by uncovering the proton affinity as a new factor and provides a new model to effectively simulate the atomic-level kinetics of heterogeneous electrochemistry.

08 HYDROGEN↗
DOE OSTI2016

Intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production [On the intrinsic selectivity and structure sensitivity of Rhodium catalysts for C 2+ oxygenate production]

Synthesis gas (CO + H 2 ) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C 2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H 2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculations using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate–adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ~6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO 2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO 2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. As a result, this work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

High-Resolution Mass Spectrometry and Molecular Characterization of Aqueous Photochemistry Products of Common Types of Secondary Organic Aerosols

A significant fraction of atmospheric organic compounds is predominantly found in condensed phases, such as aerosol particles and cloud droplets. Many of these compounds are photolabile and can degrade through direct photolysis or indirect photooxidation processes on time scales that are comparable to the typical lifetimes of aqueous droplets (hours) and particles (days). This paper presents a systematic investigation of the molecular level composition and the extent of aqueous photochemical processing in different types of secondary organic aerosol (SOA) from biogenic and anthropogenic precursors including α-pinene, β-pinene, β-myrcene, d- limonene, α-humulene, 1,3,5-trimethylbenzene, and guaiacol, oxidized by ozone (to simulate a remote atmosphere) or by OH in the presence of NOx (to simulate an urban atmosphere). Chamber- and flow tube-generated SOA samples were collected, extracted in a methanol/water solution, and photolyzed for 1 h under identical irradiation conditions. In these experiments, the irradiation was equivalent to about 3-8 h of exposure to the sun in its zenith. The molecular level composition of the dissolved SOA was probed before and after photolysis with direct-infusion electrospray ionization high-resolution mass spectrometry (ESI-HR-MS). The mass spectra of unphotolyzed SOA generated by ozone oxidation of monoterpenes showed qualitatively similar features, and contained largely overlapping subsets of identified compounds. The mass spectra of OH/NOx generated SOA had more unique visual appearance, and indicated a lower extent of products overlap. Furthermore, the fraction of nitrogen containing species (organonitrates and nitroaromatics) was highly sensitive to the SOA precursor. These observations suggest that attribution of high-resolution mass spectra in field SOA samples to specific SOA precursors should be more straightforward under OH/NOx oxidation conditions compared to the ozone driven oxidation. Comparison of the SOA constituents before and after photolysis showed the tendency to reduce the average number of atoms in the SOA compounds without a significant effect on the overall O/C and H/C ratios. SOA prepared by OH/NOx photooxidation of 1,3,5-trimethylbenzene and guaiacol were relatively resilient to photolysis despite being the most light-absorbing. The composition of SOA prepared by ozonolysis of monoterpenes changed more significantly as a result of the photolysis. The results indicate that aqueous photolysis of dissolved SOA compounds in cloud/fog water can occur in a number of SOA, and on atmospherically relevant time scales. However, the extent of change depends on the specific type of SOA.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

High-rate electroreduction of carbon monoxide to multi-carbon products

Carbon monoxide electrolysis has previously been reported to yield enhanced multi-carbon (C 2+ ) Faradaic efficiencies of up to ~55%, but only at low reaction rates. This is due to the low solubility of CO in aqueous electrolytes and operation in batch-type reactors. Here, we present a high-performance CO flow electrolyser with a well controlled electrode–electrolyte interface that can reach total current densities of up to 1 A cm –2 , together with improved C 2+ selectivities. Computational transport modelling and isotopic C 18 O reduction experiments suggest that the enhanced activity is due to a higher surface pH under CO reduction conditions, which facilitates the production of acetate. Here, at optimal operating conditions, we achieve a C 2+ Faradaic efficiency of ~91% with a C 2+ partial current density over 630 mA cm –2 . Further investigations show that maintaining an efficient triple-phase boundary at the electrode–electrolyte interface is the most critical challenge in achieving a stable CO/CO 2 electrolysis process at high rates.

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

Highly selective and productive reduction of carbon dioxide to multicarbon products via in situ CO management using segmented tandem electrodes

Electrochemical CO 2 reduction provides a promising route to the sustainable generation of valuable chemicals and fuels. Tandem catalysts enable sequential CO 2 -to-CO and CO-to-multicarbon (C 2+ ) product conversions on complementary active sites, to produce high C 2+ Faradaic efficiency (FE). Unfortunately, previous tandem catalysts exhibit poor management of CO intermediates, which diminishes C 2+ FE. Here, we design segmented gas-diffusion electrodes (s-GDEs) in which a CO-selective catalyst layer (CL) segment at the inlet prolongs CO residence time in the subsequent C 2+ -selective segment, enhancing conversion. This phenomenon enables increases in both the CO utilization and C 2+ current density for a Cu/Ag s-GDE compared to pure Cu, by increasing the *CO coverage within the Cu CL. Lastly, we develop a Cu/Fe-N-C s-GDE with 90% C 2+ FE at C 2+ partial current density (j C2+ ) exceeding 1 A cm -2 . These results prove the importance of transport and establish design principles to improve C 2+ FE and j C2+ in tandem CO 2 reduction.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2013

Neutron production using a pyroelectric driven target coupled with a gated field ionization source

A palm sized, portable neutron source would be useful for widespread implementation of detection systems for shielded, special nuclear material. We present progress towards the development of the components for an ultracompact neutron generator using a pulsed, meso-scale field ionization source, a deuterated (or tritiated) titanium target driven by a negative high voltage lithium tantalate crystal. Neutron production from integrated tests using an ion source with a single, biased tungsten tip and a 3 Multiplication-Sign 1 cm, vacuum insulated crystal with a plastic deuterated target are presented. Component testing of the ion source with a single tip produces up to 3 nA of current. Dielectric insulation of the lithium tantalate crystals appears to reduce flashover, which should improve the robustness. The field emission losses from a 3 cm diameter crystal with a plastic target and 6 cm diameter crystal with a metal target are compared.

43 PARTICLE ACCELERATORS↗
DOE OSTI2013

Lithium pellet production (LiPP): A device for the production of small spheres of lithium

With lithium as a fusion material gaining popularity, a method for producing lithium pellets relatively quickly has been developed for NSTX. The Lithium Pellet Production device is based on an injector with a sub-millimeter diameter orifice and relies on a jet of liquid lithium breaking apart into small spheres via the Plateau-Rayleigh instability. A prototype device is presented in this paper and for a pressure difference of {Delta}P= 5 Torr, spheres with diameters between 0.91 < D < 1.37 mm have been produced with an average diameter of D= 1.14 mm, which agrees with the developed theory. Successive tests performed at Princeton Plasma Physics Laboratory with Wood's metal have confirmed the dependence of sphere diameter on pressure difference as predicted.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Fusion power production in International Thermonuclear Experimental Reactor baseline H-mode scenarios

Self-consistent simulations of 15 MA ITER H-mode DT scenarios, from ramp-up through flat-top, are carried out. Electron and ion temperatures, toroidal angular frequency, and currents are evolved, in simulations carried out using the predictive TRANSPort and integrated modeling code starting with initial profiles and equilibria obtained from tokamak simulation code studies. Studies are carried out examining the dependence and sensitivity of fusion power production on electron density, argon impurity concentration, choice of radio frequency heating, pedestal temperature without and with E × B flow shear effects included, and the degree of plasma rotation. The goal of these whole-device ITER simulations is to identify dependencies that might impact ITER fusion performance.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Design and construction of a cascading pressure reactor prototype for solar-thermochemical hydrogen production

Recent work regarding the efficiency maximization for solar thermochemical fuel production in two step cycles has led to the design of a new type of reactor—the cascading pressure reactor—in which the thermal reduction step of the cycle is completed in multiple stages, at successively lower pressures. This approach enables lower thermal reduction pressures than in single-staged reactors, and decreases required pump work, leading to increased solar to fuel efficiencies. In this work we report on the design and construction of a prototype cascading pressure reactor and testing of some of the key components. We specifically focus on the technical challenges particular to the design, and their solutions.

14 SOLAR ENERGY↗
DOE OSTI2020

Optimization of laser-target parameters for the production of stable lithium beam

A laser ion source coupled with a radio frequency quadrupole linac accelerator is being proposed as a suitable system for the production of a low energy, high-current stable lithium beam. In order to maximize the lithium yield, plasmas generated by laser ablation of different materials based on lithium (Li, LiOH, and LiNbO3) have been characterized by using a Faraday cup and an electrostatic ion analyzer in the time of flight configuration. A wide range of laser power density has been investigated (109–1012 W/cm2) using two Nd:YAG lasers operating at different wavelengths (1064 nm and 532 nm), pulse durations (6 ns and 17 ns), and maximum energies (1400 mJ and 210 mJ). This paper outlines the pros and cons of the investigated materials by studying how the ion energy, yields, and charge state distributions are modified when the laser power density is changed. Considerable attention has been paid to the higher charge states of oxygen, which may occur with the same mass-to-charge ratio of Li3+. The analysis has evidenced that LiNbO3 represents a valid target since it allows minimizing the O6+/7Li3+ ratio down to 2.5% by using a laser power density of 1.8 × 1010 W/cm2. For such a condition, a Li3+ current of 1.4 mA/cm2 has been measured.

Cannavò, A. (ORCID:0000000309759630)↗