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At least 19 records

Peak‐in‐Valley Metal Nano‐Architectures via E‐Beam‐Guided Metal Oxide Redox

Focused electron beams enable nanoscale material modification via localized etching or deposition. In liquid-phase electron-beam-mediated processing, radiolysis-driven redox reactions present an opportunity to control both etching and deposition simultaneously. Here, this duality using a water-ammonia solvent as a tunable redox mediator on copper surfaces is demonstrated. At lower ammonia concentrations, the oxidation process dominates, etching copper to sub-50-nm depths. The copper ions and ion-complexes released during this initial oxidation step are reduced by solvated electrons resulting in metal deposition into the etched sites, over longer e-beam exposures, producing characteristic peak-in-valley nanostructures. Conversely, at higher ammonia concentrations copper-ammine ion complexation and radiolytic oxidizing species scavenging by ammonia occur at higher rates, creating a reducing environment conducive to rapid beam-guided copper deposition. Reaction-transport simulations and experiments are performed to show the effects of ammonia-mediated radiolysis chemistry, describing the direct influence of solvent concentration on redox balance and the outcome of e-beam guided processing. By uniting both etching and deposition within a single framework, this work provides a versatile route for controlled surface nanostructuring.

copper nanostructures↗

Highly Efficient Regeneration Module for Carbon Capture Systems in NGCC Applications

The objective of this project is to design, fabricate, and test a highly efficient regeneration module capable of providing an ultra-lean absorption solution that is required for capturing CO 2 from dilute sources at 95% or better efficiency. By integrating this advanced regenerator module with SRI International’s Mixed Salt Process (MSP) absorption modules, SRI expects to demonstrate significant progress toward a reduction in cost of capture versus the DOE reference natural gas combined cycle (NGCC) plant with carbon capture. SRI designed, built, and tested an advanced stripper to enhance the performance of SRI’s MSP for CO 2 capture – a transformational ammonia-based solvent technology – for natural gas (NG) power sources. The testing of the advanced stripper for MSP was conducted at an SRI site using a simulated flue gas stream equivalent to about 10 kWe. The research work included modeling of the advanced stripper and integrating it with the MSP absorbers; studying the strategies for producing very highly alkaline lean solvent with minimized emissions; operating the stripper with advanced heat integration to improve process efficiencies; and collecting critically important data for a detailed techno-economic analysis (TEA). The project tasks were designed to address concerns relating to scale-up and integration of the technology to NG power plants—more specifically, to maximize the carbon capture efficiency achievable with MSP and identify pathways to achieve higher capture efficiencies and ultimately zero net carbon emissions. SRI teamed up with a process modeling company (OLI Systems), a process and chemical engineering company (Trimeric Corporation), and a cost-sharing commercial partner (Baker-Hughes – a leading multinational company that designs, manufactures, and services transformative energy technologies) to execute the project. The research findings will accelerate the MSP development and pave the way for the technology to reach the DOE’s goal, and ultimately commercialization of the MSP technology for low-cost CO 2 capture from NGCC flue gas and other dilute CO 2 sources.

03 NATURAL GAS↗

Universal Reversible Hydrogen Potential for Electrocatalytic Ammonia Splitting Reactions in Nonaqueous Solvents from Unified pH Measurements

In this work, we introduce a new approach of using differential potentiometric measurements in four nonaqueous solvents─MeCN, THF, DMF, and PC─to determine the universal pH abs H 2 O values aligned to the aqueous pH scale for dilute NH 4 + /NH 3 solutions. Knowledge of the pH abs H 2 O values allows simple determination of the reversible hydrogen potential in any given solvent relative to the aqueous standard hydrogen electrode (SHE) and, most importantly, ensures comparability across different solvents. As an independent method, Open Circuit Potenial measurements were carried out in the same solvents titrated with NH 4 + /NH 3 to obtain alternative values for the reversible hydrogen potential in these solvents. The close agreement of these two methods, as well as calculated potentials from literature values when available, substantiates the new, simpler, and more robust approach to determine the reversible hydrogen potential introduced here. We further use the reversible hydrogen potential values established here to report, for the first time, the overpotential for ammonia oxidation as a function of solvent, with a recently discovered ruthenium catalyst.

ammonia↗

Coordination Chemistry of Solvated Metal Ions in Soft Donor Solvents

The structures of hexaammine solvated indium(III) and thallium(III) ions in liquid ammonia solution are determined by EXAFS. Both complexes have regular octahedral coordination geometry with mean In-N and Tl-N bond distances of 2.23(1) and 2.29(2) Å, respectively. Ammine solvated thallium(III) in liquid ammonia is characterized with 205Tl NMR measurements. Solvents such as liquid ammonia, N,N-dimethylthioformamide (DMTF), trialkyl and triphenyl phosphite and phosphine are strong electron pair donors and thereby able to form bonds with a large covalent contribution with strong electron pair acceptors. A survey of reported structures of ammine, DMTF, trialkyl and triphenyl phosphite and phosphine solvated metal ions in the solid state and solution is presented. The M-N and M-S bond distances in ammine and DMTF solvated metal ions are compared with the M-O bond distance in the corresponding metal ion hydrates, expected to form mainly electrostatic interactions with metal ions. The d10 metal ions have high ability to form bonds with a high degree of covalency with increasing ability down the group and with decreasing charge of the metal ion. The difference in M-N and M-O bond distances between ammine solvated and hydrated metal ions with the same coordination geometry decreases significantly with the increasing ability of the metal ion to form bonds with a large covalent contribution. This difference correlates well with the covalent bonding index, γM2*r.

Biochemistry & Molecular Biology↗

Corona-discharge air-purification system

Plasma reaction chamber removes trace contaminants from spacecraft, submarines, and other closed environments by oxidizing contaminants to produce carbon dioxide and water. Contaminants are alcohols, esters, hydrogen sulfide, and ammonia. Others are lubricant solvents such as Freons, aromatics, and Ketones. Contaminants are removed from chamber by scrubber.

Wydeven, T. J.↗

Preparation of B-trichloroborazine

The present invention relates to a method of preparing B-trichloroborazine. Generally, the method includes the combination of gaseous boron trichloride in an anhydrous aprotic organic solvent followed by addition of excess gaseous ammonia at ambient temperature or below. The reaction mixture is heated to about 100 to 140 C followed by cooling, removal of the solid ammonium chloride at ambient temperature, distillation of the solvent under vacuum if necessary at a temperature of up to about 112 C, and recovery of the B-trichloroborazine. Solvents include toluene, benzene, xylene, chlorinated hydrocarbons, chlorinated aromatic compounds, or mixtures thereof. Toluene is a preferred solvent. The process provides a convenient synthesis of a material which often decomposes on standing. B-trichloroborazine is useful in a number of chemical reactions, and particularly in the formation of high temperature inorganic polymers and polymer precursors.

Riccitiello, Salvatore R.↗

Two Catalysts for Selective Oxidation of Contaminant Gases

Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to nitrogen at temperatures up to 400 C, without producing nitrogen oxides. This catalyst converts ammonia completely to nitrogen, even when the concentration of ammonia is very low. No other catalyst is known to oxidize ammonia selectively at such a high temperature and low concentration. Both the metal oxide and the support contribute to the activity and selectivity of this catalyst.

Wright, John D.↗

Process for producing an activated carbon adsorbent with integral heat transfer apparatus

A process for producing an integral adsorbent-heat exchanger apparatus useful in ammonia refrigerant heat pump systems. In one embodiment, the process wets an activated carbon particles-solvent mixture with a binder-solvent mixture, presses the binder wetted activated carbon mixture on a metal tube surface and thereafter pyrolyzes the mixture to form a bonded activated carbon matrix adjoined to the tube surface. The integral apparatus can be easily and inexpensively produced by the process in large quantities.

Jones, Jack A.↗

Ammonium Looping with Membrane Absorber and Distributed Stripper for Enhanced Algae Growth

The objective of this project is to conduct a comprehensive investigation to develop and demonstrate a practical, reliable, and cost-effective integrated carbon dioxide (CO 2 ) capture and biofixation process for algae production. This process utilizes a chemical hindered ammonium solution (NH 4 OH) as both a capture reagent and an algae nutrient. The membrane absorber employed in the system ensured minimal ammonia (NH 3 ) emissions in the treated flue gas. Additionally, distributed solar-energy powered strippers located near the bioreactor modules facilitate solvent regeneration and enable just-in-time delivery of CO 2 and NH 3 to the algae, thereby minimizing the pH swing for enhanced productivity. The proposed membrane CO 2 absorber and solar-powered stripper is designed and seamlessly integrated with the existing 0.1 MWth bench-scale CO 2 capture system (CCS) and open raceway ponds (ORPs) at the University of Kentucky Center for Applied Energy (UK CAER) campus. The entire integrated process has undergone construction, operation, testing, and analysis. Furthermore, technology has been evaluated with a techno-economic analysis (TEA), technology gap analysis (TGA), life-cycle analysis (LCA), and a technology maturation plan (TMP). This project was performed within two budget periods, 54 months in duration. There are fourteen Project Tasks, twelve Milestones and four Success Criteria.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adaptation of an Ammonia Detecting Paint to Commerical Applications

An ammonia-sensitive coating was developed in feasibility studies sponsored by Lockheed Engineering. The paint comprised a cellulosic binder, a dye, a family of solvents, and plasticizer. The resulting coating formulation proved to be very sensitive to trace levels of Lewis-bases and/or nucleophiles, but was limited to concentrations of approximately 1 ppm and higher. In the months following completion of this Lockheed project, efforts to perfect and optimize the paint formulation continued with internal funding. A unique sensitivity enhancing additive was identified and patented which when applied at concentrations of approximately 10% by weight, transcended the 1 ppm sensitivity barrier to fractional ppb. The paint composition was modified by the addition of certain proprietary agents, which promoted a much more intense yellow color in the coating and enhanced its durability in high-vacuum. Paint preparation is a simple one day procedure that can be completed using conventional equipment. Most of the materials are easily obtained.

Graef, Renee C.↗

Crystal growing by electrodeposition from dense gaseous solutions

Single crystals and dendritic formations of silver are grown on platinum electrodes by electrodeposition from a dense gaseous solution of silver nitrate in ammonia. Process is modification of hydrothermal process, and also differs from standard electrodeposition by permitting single crystals to be grown from hydrogen-bonded solvents.

Naiditch, S.↗

Preparation of perfluorinated 1,2,4-oxadiazoles

Fluorinated alkyl or alkylether 1,2,4 oxadiazole compounds are prepared by cyclizing the corresponding alkyl or alkylether imidoyl amidoximes in vacuo or in an inert atmosphere at a temperature within the range of 40 C to 100 C. for a period of 8 to 144 hours in the presence of an acid compound which can accept ammonia to form a salt. The imidoyl amidoximes usable in this process are either polymeric or nonpolymeric. The products, when polymeric, have excellent heat, chemical and solvent resistance.

Kratzer, R. H.↗

A Theoretical Investigation of the Plausibility of Reactions Between Ammonia and Carbonyl Species (Formaldehyde, Acetaldehyde, and Acetone) in Interstellar Ice Analogs at Ultracold Temperatures

We have reexamined the reaction between formaldehyde and ammonia, which was previously studied by us and other workers in modestly sized cluster calculations. Larger model systems with up to 12H2O were employed, and reactions of two more carbonyl species, acetaldehyde and acetone, were also carried out. Calculations were performed at the B3LYP/6-31+G** level with bulk solvent effects treated with a polarizable continuum model; limited MP2/6-31+G** calculations were also performed. We found that while the barrier for the concerted proton relay mechanism described in previous work remains modest, it is still prohibitively high for the reaction to occur under the ultracold conditions that prevail in dense interstellar clouds. However, a new pathway emerged in more realistic clusters that involves at least one barrierless step for two of the carbonyl species considered here: ammonia reacts with formaldehyde and acetaldehyde to form a partial charge transfer species in small clusters (4H2O) and a protonated hydroxyamino intermediate species in large clusters (9H2O, 12H2O); modest barriers that decrease sharply with cluster size are found for the analogous processes for the acetone-NH3 reaction. Furthermore, if a second ammonia replaces one of the water molecules in calculations in the 9H2O clusters, deprotonation can occur to yield the same neutral hydroxyamino species that is formed via the original concerted proton relay mechanism. In at least one position, deprotonation is barrierless when zero-point energy is included. In addition to describing the structures and energetics of the reactions between formaldehyde, acetaldehyde, and acetone with ammonia, we report spectroscopic predictions of the observable vibrational features that are expected to be present in ice mixtures of different composition.

Chen, Lina↗

A new method for the preparation of polymeric porous layer open tubular columns for GC application

A new method to prepare polymeric PLOT columns by using in situ polymerization technology is described. The method involves a straightforward in situ polymerization of the monomer. The polymer produced is directly coated on the metal tubing. This eliminates many of the steps needed in conventional polymeric PLOT column preparation. Our method is easy to operate and produces very reproducible columns, as shown previously (T. C. Shen. J. Chromatogr. Sci. 30, 239, 1992). The effects of solvents, tubing pretreatments, initiators and reaction temperatures in the preparation of PLOT columns are studied. Several columns have been developed to separate (1) highly polar compounds, such as water and ammonia or water and HCN, and (2) hydrocarbons and inert gases. A recent improvement has allowed us to produce bonded polymeric PLOT columns. These were studied, and the results are included also.

NASA Discipline Exobiology↗

Isotopic analyses of nitrogenous compounds from the Murchison meteorite: ammonia, amines, amino acids, and polar hydrocarbons

The combined volatile bases (ammonia, aliphatic amines, and possibly other bases), ammonia, amino acids, and polar hydrocarbons were prepared from the Murchison meteorite for isotopic analyses. The volatile bases were obtained by cryogenic transfer after acid-hydrolysis of a hot-water extract and analyzed by combined gas chromatography-mass spectrometry of pentafluoropropionyl derivatives. The aliphatic amines present in this preparation comprise a mixture that includes both primary and secondary isomers through C5 at a total concentration of > or = 100 nmoles g-1. As commonly observed for meteoritic organic compounds, almost all isomers through C5 are present, and the concentrations within homologous series decrease with increasing chain length. Ammonia was chromatographically separated from the other volatile bases and found at a concentration of 1.1-1.3 micromoles g-1 meteorite. The ammonia analyzed includes contributions from ammonium salts and the hydrolysis of extractable organic compounds, e.g., carboxamides. Stable isotope analyses showed the volatile bases to be substantially enriched in the heavier isotopes, relative to comparable terrestrial compounds delta D < or = +1221%; delta 13C = +22%; delta 15N = +93%). Ammonia, per se, was found to have a somewhat lower delta 15N value (+69%) than the total volatile bases; consequently, a higher delta 15N (>93%) can be inferred for the other bases, which include the amines. Solvent-extractable polar hydrocarbons obtained separately were found to be enriched in 15N (delta 15N = +104%). Total amino acids, prepared from a hydrolyzed hot-water extract by cation exchange chromatography, gave a delta 15N of +94%, a value in good agreement with that obtained previously. Nitrogen isotopic data are also given for amino acid fractions separated chromatographically. The delta 15N values of the Murchison soluble organic compounds analyzed to date fall within a rather narrow range (delta 15N = +94 +/- 8%), an observation consistent with their formation, or formation of their precursors, by interstellar chemistry.

Non-NASA Center↗