Results for “reactive absorption” — Page 13

DOE OSTI2021

Understanding Selectivity in CO2 Hydrogenation to Methanol for MoP Nanoparticle Catalysts Using In Situ Techniques

Molybdenum phosphide (MoP) catalyzes the hydrogenation of CO, CO2, and their mixtures to methanol, and it is investigated as a high-activity catalyst that overcomes deactivation issues (e.g., formate poisoning) faced by conventional transition metal catalysts. MoP as a new catalyst for hydrogenating CO2 to methanol is particularly appealing for the use of CO2 as chemical feedstock. Herein, we use a colloidal synthesis technique that connects the presence of MoP to the formation of methanol from CO2, regardless of the support being used. By conducting a systematic support study, we see that zirconia (ZrO2) has the striking ability to shift the selectivity towards methanol by increasing the rate of methanol conversion by two orders of magnitude compared to other supports, at a CO2 conversion of 1.4% and methanol selectivity of 55.4%. In situ X-ray Absorption Spectroscopy (XAS) and in situ X-ray Diffraction (XRD) indicate that under reaction conditions the catalyst is pure MoP in a partially crystalline phase. Results from Diffuse Reflectance Infrared Fourier Transform Spectroscopy coupled with Temperature Programmed Surface Reaction (DRIFTS-TPSR) point towards a highly reactive monodentate formate intermediate stabilized by the strong interaction of MoP and ZrO2. This study definitively shows that the presence of a MoP phase leads to methanol formation from CO2, regardless of support and that the formate intermediate on MoP governs methanol formation rate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2000

Simulation and Experimental Measurements of Inductively Coupled CF4 and CF4/Ar Plasmas

The recently developed code SEMS (semiconductor equipment modeling software)is applied to the simulation of CF4 and CF4/Ar inductively coupled plasmas (ICP). This work builds upon the earlier nitrogen, transformer coupled plasma (TCP) SEMS research by demonstrating its accuracy for more complex reactive mixtures, moving closer to the realization of a virtual plasma reactor. Attention is given to the etching of and/or formation of carbonaceous films on the quartz dielectric window and diagnostic aperatures. The simulations are validated through comparisons with experimental measurements using FTIR (Fourier Transform Infrared) and UV absorption spectroscopy for CFx and SiFx neutral radicals, QMS (quadrupole mass spectrometry) for the ions, and Langmuir probe measurements of electron number density and temperature in an ICP GEC reference cell.

Hash, D. B.↗

NASA NTRS2001

Preparation and Preliminary Characterization of Crystallizing Fluorescent Derivatives of Chicken Egg White Lysozyme

Fluorescence is one of the most versatile and powerful tools for the study of macromolecules. While most proteins are intrinsically fluorescent, working at crystallization concentrations require the use of covalently prepared derivatives added as tracers. This approach requires derivatives that do not markedly affect the crystal packing. We have prepared fluorescent derivatives of chicken egg white lysozyme with probes bound to one of two different sites on the protein molecule. Lucifer yellow and 5-(2-aminoethyl)aminonapthalene-1-sulfonic acid (EDANS) have been attached to the side chain carboxyl of Asp(sup 101) using a carbodiimide coupling procedure. Asp(sup 101) lies within the active site cleft, and it is believed that the probes are "buried" within that cleft. Lucifer yellow and MANS probes with iodoacetamide reactive groups have been bound to His(sup 15), located on the "back side" of the molecule relative to the active site. All the derivatives fluoresce in the solution and the crystalline states. Fluorescence characterization has focused on determination of binding effects on the probe quantum yield, lifetime, absorption and emission spectra, and quenching by added solutes. Quenching studies show that, as postulated, the Asp(sup 101)-bound probes are partially sheltered from the bulk solution by their location within the active site cleft. Probes bound to His(sup 15) have quenching constants about equal to those for the free probes, indicating that this site is highly exposed to the bulk solution.

Sumida, John↗

DOE OSTI2025

Tuning Catalytic Reactivity via Wetting Control through Oxygen Vacancies: Ru Clusters on Anatase TiO 2 and CeO 2 Supports

The shape of supported metal particles regulates their catalytic reactivity and is determined by the degree of wetting between the metal particle and the support surface. Flattened particles that wet support surfaces were reported in various catalytic systems, particularly in the subnanometer size regime. Such consequential metal–support wetting phenomena are poorly understood, and methods to study them on powder catalysts under realistic conditions are lacking. Here, we investigate the size-dependent wetting behaviors of Ru particles on two reducible-oxide supports, anatase TiO 2 (TiO 2 -A) and CeO 2 , under reducing catalytic conditions. X-ray absorption spectroscopy (XAS), low-energy ion scattering (LEIS), and density functional theory (DFT) are combined to determine the shape of Ru particles. Ru particles remain three-dimensional without wetting the TiO 2 -A support within the coverage range studied (0.06–0.98 Ru nm –2 ). In contrast, at low coverages (<0.25 Ru nm –2 ), Ru wets the CeO 2 support to form flat, disordered structures. The higher wettability of CeO 2 than TiO 2 -A is attributed to oxygen vacancies in the near-surface region. The shape difference between small Ru particles or clusters on the two supports leads to drastically contrasting catalytic reactivities in polyolefin hydrogenolysis, despite similar diameters. As a result, this work highlights the implications of metal–support wetting, or cluster shape, on catalytic behaviors of small metal clusters, while establishing the foundation for future systematic studies of such a phenomenon in realistic systems, by delivering a multitechnique methodology and revealing governing fundamental principles.

42 ENGINEERING↗

DOE OSTI2020

Enhanced Arsenic (III and V) Removal in Anoxic Environments by Hierarchically Structured Citrate/FeCO 3 Nanocomposites

Novel citrate/FeCO 3 nanocomposites (CF-NCs) were synthesized for effective arsenic (III and V) sorption with constant addition of Fe2+ into HCO 3 - solution in the presence of citrate. This paper is the first report on the formation of CF-NCs, and in this study we investigate the mechanisms of arsenic uptake by the sorbent under anoxic conditions through various solid- and liquid-phase spectroscopic methods, including X-ray absorption spectroscopy. In CF-NCs, citrate was found to be incorporated into the structure of siderite (up to 17.94%) through (Fe 2+ citrate) - complexes. The crystal morphology of rhombohedral siderite was changed into hierarchically nanostructured spherical aggregates composed of several sheet-like crystals, which improved the surface reactivity in the presence of sufficient citrate. Compared to pure siderite (15.2%), enhanced removal of As(III) in the range of 19.3% to 88.2% was observed, depending on the amount of incorporated citrate. The maximum sorption capacities of CF-NCs for As(III) and As(V) were 188.97 and 290.22 mg/g, respectively, which are much higher than those of previously reported siderite-based adsorbents. It was found that arsenic (III and V) sorption on CF-NCs occurred via bidentate corner-sharing surface complexation, predominantly without changes in the arsenic oxidation states. These results suggest that arsenic (III and V) can be attenuated by siderite in anoxic environments, and this attenuation can be even more effective when siderite is modified by incorporation of organic compounds such as citrate.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2001

Preparation and Preliminary Characterization of Crystallizing Fluorescent Derivatives of Chicken Egg White Lysozyme

Fluorescence is one of the most versatile and powerful tools for the study of macromolecules. While most proteins are intrinsically fluorescent, working at crystallization concentrations require the use of covalently prepared derivatives added as tracers. This approach requires derivatives that do not markedly affect the crystal packing. We have prepared fluorescent derivatives of chicken egg white lysozyme with probes bound to one of two different sites on the protein molecule. Lucifer yellow and 5-(2-aminoethyl)aminonapthalene-i-sulfonic acid (EDANS) have been attached to the side chain carboxyl of Asp(sup 101) using a carbodiimide coupling procedure. Asp(sup 101) lies within the active site cleft, and it is believed that the probes are 'buried' within that cleft. Lucifer yellow and MANS probes with iodoacetamide reactive five groups have been bound to His(sup 15), located on the 'back side' of the molecule relative to the active site. All the derivatives fluoresce in the solution and the crystalline states. Fluorescence characterization has focused on determination of binding effects on the probe quantum yield, lifetime, absorption and emission spectra, and quenching by added solutes. Quenching studies show that, as postulated, the Asp(sup 101)-bound probes are partially sheltered from the bulk solution by their location within the active site cleft. Probes bound to His(sup 15) have quenching constants about equal to those for the free probes, indicating that this site is highly exposed to the bulk solution.

Sumida, John P.↗

NASA NTRSDate not supplied

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)↗

NASA NTRSDate not supplied

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)↗

NASA NTRSDate not supplied

Enhanced Far Ultra-Violet Optical Properties of Physical Vapor Deposited Aluminum Mirrors Through Fluorination

Astronomical instrumentation for measurements in the Far Ultra-Violet (FUV, 90-200 nm) typically use aluminum (Al) thin films due to their high reflectance over this wavelength range. However, the native aluminum oxide layer that forms on Al upon exposure to the atmosphere is strongly absorbing in this wavelength range, requiring that the films be protected with a dielectric that inhibits oxidation. Typically, magnesium fluoride (MgF 2 ) or lithium fluoride (LiF) coatings are used as protective layers, but each has shortcomings. For example, MgF 2 has an absorption cutoff at 115 nm reducing performance in a critical part of the FUV spectrum of observational interest. A viable option to access these lower wavelengths could be the use of the LiF overcoat as it has a lower absorption cutoff at 102.5 nm, but it is hygroscopic and thus susceptible to degradation in humid conditions. An approach to reduce the hygroscopic nature of LiF would be to implement a passivation process during the deposition of both Al+LiF coatings. Our team at GSFC has developed a new reactive Physical Vapor Deposition (rPVD) process that consists of a fluorination process with XeF 2 gas combined with our traditional PVD process. We have found that this new rPVD coating process offers a protected version of Al+LiF with a more environmentally stable and more transparent LiF layer, along with unprecedent reflectivity. The process starts with a bare optically smooth substrate that is coated with Al in an ultra-high vacuum (UHV) chamber by the conventional PVD process. Then, the bare Al mirror is immediately exposed to a reactive XeF 2 gas before and after the application of the flash PVD evaporated LiF layer. We have also been investigating the use of this rPVD coating process for potential efficiency enhancements of Si-based gratings. Since it is known that the XeF 2 vapor is a strong Si etchant, we are investigating if the native SiO 2 layer on Si is sufficient to protect the groove profile of e-beam-ruled Si gratings from degradation. We will report on the characterization of various Al+LiF witness mirror coatings (both on borosilicate and Si) performed under various deposition conditions using the XeF 2 passivation process. These tests include XPS to determine film stoichiometry and AFM/SEM to measure surface roughness and any etching on the Si substrate. We will also report on FUV reflectance and spectroscopic ellipsometry to characterize optical constants of these passivated films in the UV/Visible/NIR spectral ranges.

Engineering (General)↗

NASA NTRS2013

1,2-Dichlorohexafluoro-Cyclobutane (1,2-c-C4F6Cl2, R-316c) a Potent Ozone Depleting Substance and Greenhouse Gas: Atmospheric Loss Processes, Lifetimes, and Ozone Depletion and Global Warming Potentials for the (E) and (Z) stereoisomers

The atmospheric processing of (E)- and (Z)-1,2-dichlorohexafluorocyclobutane (1,2-c-C4F6Cl2, R-316c) was examined in this work as the ozone depleting (ODP) and global warming (GWP) potentials of this proposed replacement compound are presently unknown. The predominant atmospheric loss processes and infrared absorption spectra of the R-316c isomers were measured to provide a basis to evaluate their atmospheric lifetimes and, thus, ODPs and GWPs. UV absorption spectra were measured between 184.95 to 230 nm at temperatures between 214 and 296 K and a parametrization for use in atmospheric modeling is presented. The Cl atom quantum yield in the 193 nm photolysis of R- 316c was measured to be 1.90 +/- 0.27. Hexafluorocyclobutene (c-C4F6) was determined to be a photolysis co-product with molar yields of 0.7 and 1.0 (+/-10%) for (E)- and (Z)-R-316c, respectively. The 296 K total rate coefficient for the O(1D) + R-316c reaction, i.e., O(1D) loss, was measured to be (1.56 +/- 0.11) × 10(exp −10)cu cm/ molecule/s and the reactive rate coefficient, i.e., R-316c loss, was measured to be (1.36 +/- 0.20) × 10(exp −10)cu cm/molecule/s corresponding to a approx. 88% reactive yield. Rate coefficient upper-limits for the OH and O3 reaction with R-316c were determined to be <2.3 × 10(exp −17) and <2.0 × 10(exp −22)cu cm/molecule/s, respectively, at 296 K. The quoted uncertainty limits are 2(sigma) and include estimated systematic errors. Local and global annually averaged lifetimes for the (E)- and (Z)-R-316c isomers were calculated using a 2-D atmospheric model to be 74.6 +/- 3 and 114.1 +/-10 years, respectively, where the estimated uncertainties are due solely to the uncertainty in the UV absorption spectra. Stratospheric photolysis is the predominant atmospheric loss process for both isomers with the O(1D) reaction making a minor, approx. 2% for the (E) isomer and 7% for the (Z) isomer, contribution to the total atmospheric loss. Ozone depletion potentials for (E)- and (Z)-R-316c were calculated using the 2-D model to be 0.46 and 0.54, respectively. Infrared absorption spectra for (E)- and (Z)-R-316c were measured at 296 K and used to estimate their radiative efficiencies (REs) and GWPs; 100-year time-horizon GWPs of 4160 and 5400 were obtained for (E)- and (Z)-R-316c, respectively. Both isomers of R-316c are shown in this work to be long-lived ozone depleting substances and potent greenhouse gases.

UV cross section↗

DOE OSTI2021

Electronic and structural properties of single-crystal Jahn–Teller active Co 1+x Mn 2–x O 4 thin films

Recent investigations on spinel CoMn 2 O 4 have shown its potential for applications in water splitting and fuel cell technologies as it exhibits strong catalytic behavior through oxygen reduction reactivity. To further understand this material, we report for the first time the synthesis of single-crystalline Co 1+x Mn 2-x O 4 thin films using molecular beam epitaxy. By varying sample composition, we establish links between cation stoichiometry and material properties using in-situ x-ray photoelectron spectroscopy, x-ray diffraction, scanning transmission electron microscopy, x-ray absorption spectroscopy, and spectroscopic ellipsometry. Our results indicate that excess Co ions occupy interstitial tetrahedral sites up to a certain stoichiometry, then are substitutional for octahedrally-coordinated Mn beyond this threshold. Here, we compare these results with density functional theory models of stoichiometric CoMn 2 O 4 to understand how the Jahn-Teller distortion and hybridization in Mn-O bonds impact the ability to hole dope the material with excess Co. The findings provide important insights into CoMn 2 O 4 and related spinel oxides for future application as inexpensive oxygen reduction reaction catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1975

Decomposition of NO studied by infrared emission and CO laser absorption

A diagnostic technique for monitoring the concentration of NO using absorption of CO laser radiation has been developed and applied in a study of the decomposition kinetics of NO. Simultaneous measurements of infrared emission by NO at 5.3 microns were also made to validate the laser absorption technique. The data were obtained behind incident shocks in NO-N2O-Ar (or Kr) mixtures, with temperatures in the range 2400-4100 K. The rate constant for the dominant reaction of O and NO to yield N and O2 was inferred from comparisons with computer simulations of the reactive flow.

Hanson, R. K.↗

DOE OSTI2025

Ultrafast optical modulation of vibrational strong coupling in ReCl(CO) 3 (2,2-bipyridine)

Polaritons – hybrid light-matter states formed from the strong coupling of a bright molecular transition with a confined photonic mode – may offer new opportunities for optical control of molecular behavior. Vibrational strong coupling (VSC) has been reported to impact ground-state chemical reactivity, but its influence on electronic excited-state dynamics remains unexplored. Here, we take a first step towards excited-state VSC by demonstrating optical modulation of the ReCl(CO) 3 (bpy), (bpy = 2,2-bipyridine) complex under VSC using femtosecond ultraviolet (UV)-pump/infrared (IR)-probe spectroscopy. We establish ground-state VSC of ReCl(CO) 3 (bpy) in a microfluidic Fabry-Pérot cavity equipped with indium tin oxide (ITO)-coated mirrors. ITO is effectively dichroic as it is reflective in the IR and transmissive in the UV-visible and therefore minimizes optical interference. Excitation with UV pump light drives ReCl(CO) 3 (bpy) into a manifold of electronic excited states that subsequently undergo non-radiative relaxation dynamics. We probe the transient response of the strongly-coupled system in the mid-IR, observing both Rabi contraction and cavity-filtered excited-state absorption signatures. We reconstruct the intrinsic response of intracavity molecules from the transient cavity transmission spectra to enable quantitative comparison with extracavity control experiments. We report no changes in the excited-state dynamics of ReCl(CO) 3 (bpy) under ground-state VSC. However, we do observe significant amplification of transient vibrational signals due to classical cavity-enhanced optical effects. This effort lays the groundwork to pursue direct excited-state VSC aimed at modulating photochemical reactivity.

cavity-enhanced spectroscopy↗

DOE OSTI2023

Observations of Ethylene-for-CO Ligand Exchanges on a Zeolite-Supported Single-Site Rh Catalyst by X-ray Absorption Spectroscopy

Quick-scanning X-ray absorption fine structure (QXAFS) measurements were used to characterize the exchanges of ethylene and CO ligands in a zeolite HY-supported single-site Rh complex at a sampling rate of 1.0 Hz. The two ligands were reversibly exchanged on the rhodium, with quantitative results determined for the C 2 H 4 -for-CO exchange that are consistent with a first-order process. The apparent rate constant for the exchange decreased with increasing temperature. Fourier-transform infrared spectra characterizing the C 2 H 4 sorbed in the zeolite showed that the amount decreased with increasing temperature, consistent with the decrease in the exchange rate with increasing temperature. Here the results, illustrating the dynamics of ligand exchanges on a single-site supported metal catalyst, demonstrate the broad emerging applicability of the QXAFS technique for characterizing the dynamics of reactive intermediates on catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Tailoring Electrochemical CO 2 Reduction on Copper by Reactive Ionic Liquid and Native Hydrogen Bond Donors

Abstract Electrochemical CO 2 reduction (CO 2 RR) on copper (Cu) shows promise for higher‐value products beyond CO. However, challenges such as the limited CO 2 solubility, high overpotentials, and the competing hydrogen evolution reaction (HER) in aqueous electrolytes hinder the practical realization. We propose a functionalized ionic liquid (IL) which generates ion‐CO 2 adducts and a hydrogen bond donor (HBD) upon CO 2 absorption to modulate CO 2 RR on Cu in a non‐aqueous electrolyte. As revealed by transient voltammetry, electrochemical impedance spectroscopy (EIS), and in situ surface‐enhanced Raman spectroscopy (SERS) complemented with image charge augmented quantum‐mechanical/molecular mechanics (IC‐QM/MM) computations, a unique microenvironment is constructed. In this microenvironment, the catalytic activity is primarily governed by the IL and HBD concentrations; former controlling the double layer thickness and the latter modulating the local proton availability. This translates to ample CO 2 availability, reduced overpotential, and suppressed HER where C 4 products are obtained. This study deepens the understanding of electrolyte effects in CO 2 RR and the role of IL ions towards electrocatalytic microenvironment design.

Coskun, Oguz Kagan↗

DOE OSTI2020

Vanadyl Phosphates A x VOPO 4 (A = Li, Na, K) as Multielectron Cathodes for Alkali-Ion Batteries

Vanadyl phosphates comprise a class of multielectron cathode materials capable of cycling two Li + , about 1.66 Na + , and some K + ions per redox center. In this review, structures, thermodynamic stabilities, and ion diffusion kinetics of various A x VOPO 4 (A = Li, Na, K, NH 4 ) polymorphs are discussed. Both the experimental data and first-principle calculations indicate kinetic limitations for alkali metal ions cycling, especially between for 0 ≤ x ≤ 1, and metastability of phases with x > 1. This creates challenges for multiple-ion cycling, as the slow kinetics call for nanosized particles, which being metastable and reactive with organic electrolytes are prone to side reactions. Thus, various synthesis approaches, surface coating, and transition metal ion substitution strategies are discussed here as possible ways to stabilize A x VOPO 4 structures and improve alkali metal ion diffusion. Finally, the role of advanced characterization techniques, such as X-ray absorption spectroscopy, diffraction, pair distribution function analysis and 7 Li and 31 P NMR, in understanding the reaction mechanism from both structural and electronic points of view is emphasized.

25 ENERGY STORAGE↗

NASA NTRS1977

Formulation of electrically conductive, thermal-control coatings

Formulation of electrically conductive, thermal-control coatings was undertaken for use on the International Sun Earth Explorer (ISEE) spacecraft. Unsuccessful formulation efforts as well as the successful use of oxide pigments fired at 1175 C are described. Problems attributed to reactivity of specific coating vehicles exposed to high humidity are discussed. Measurement and testing methods, including resulting data are mentioned, but the emphasis, in this report, is placed on coating formulation and application techniques. Methods of varying, as desired, optical properties are also described as well as formulations of white, low-absorptance coatings.

Shai, M. C.↗

NASA NTRS1986

The determination of the global average OH concentration using a deuteroethane tracer

It is proposed to measure the decreasing global concentration of an OH reactive isotopic tracer, G sub 2 D sub 6, after its introduction into the troposphere in a manner to facilitate uniform global mixing. Analyses at the level of 2 x 10 to the -19th power fraction, corresponding to one kg uniformly distributed globally, should be possible by a combination of cryogenic absorption techniques to separate ethane from air and high sensitivity isotopic analysis of ethane by mass spectrometry. Aliquots of C sub 2 D sub 6 totaling one kg would be introduced to numerous southern and northern latitudes over a 10 day period in order to achieve a uniform global concentration within 3 to 6 months by the normal atmospheric circulation. Then samples of air of 1000 l (STP) would be collected periodically at a tropical and temperate zone location in each hemisphere and spiked with a known amount of another isotopic species of ethane, C-13 sub 2 H sub 6, at the level of 10 to the -11th power mole fraction. After separation of the ethanes from air, the absolute concentration of C sub 2 D sub 6 would be analyzed using the Argonne 100-inch radius mass spectrometer.

Stevens, Charles M.↗