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All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Distribution of desert varnish in Arizona

Desert varnish is the dark coat of clay and ferromanganese oxides developed on exposed rock surfaces in arid regions. It forms from the accretion of material from windblown dust. The distribution of desert varnish was mapped in Arizona. It was discovered that desert varnish could be mapped on a regional scale. Well developed desert varnish is common on stable rock surfaces in areas having alkaline soils and less than about 25 cm of annual precipitation. Rock surfaces in areas having more than 40 cm of annual precipitation are generally devoid of desert varnish. An experiment was conducted with varnished desert pavement stone. The stones were broken in half and half was set on a roof in central Illinois from April until October. Removed from the alkaline desert environment, it only took seven months for the varnish to develop an eroded appearance. This experiment graphically illustrates the dependency of desert varnish on alkalinity. In this context, the zones of eroded desert varnish in Arizona indicate that the area of active desert varnish formation has fluctuated, expanding in drier times and contracting/eroding in wetter times.

Elvidge, Christopher D.↗
DOE OSTI2020

Coupled Hydrothermal Extraction and Ligand-Associated Swellable Glass Media Recovery of Rare Earth Elements from Coal Fly Ash (Final Report)

Wayne State University (WSU) researchers, in collaboration with the University of California-Los Angeles (UCLA) and Los Alamos National Laboratory (LANL), have successfully developed a new sorbent media used in a process that concentrated the rare earth content in a coal fly ash sample from southeast MI by >350×, resulting in >13 wt% REO powder. The project developed a new DTPA-associated media that was used to concentrate total REEs. This project demonstrated a coupled hydrothermal extraction and solid-liquid recovery process that produced REO powder from raw fly ash while nearly eliminating the use of organic solvents. The project successfully: 1) identified a commercially viable ash supply with >$2.5 M in REO value being deposited monthly, 2) hydrothermally extracted >77% of REEs in coal fly ash (20% more than acid alone), 3) developed a new sorbent media that was used to concentrate REEs, 4) and engineered a process that resulted in a >13 wt% REO powder. The media also demonstrates a selectivity for mid and heavy REEs over Ce and La and the potential for use in separating individual rare earth elements. An invention disclosure for the sorbent media has been filed with WSU and a patent application will be submitted in the near future. The project examined the potential to couple hydrothermal leaching of coal fly ash with the engineering of a custom ligand-associated media to provide an organic solvent-free method of extracting and recovering REEs. Fly ash feedstock was collected from Detroit area coal-fired power plants, characterized for REE content, and subjected to a bench-top batch hydrothermal leaching/dissolution process inside custom-build pressure reactors at Los Alamos National Laboratory (LANL). This process applied a dissolution technique previously developed to process spent nuclear fuel and other nuclear materials. The modified ash was acidified and the resulting leachate was enriched with REEs along with Ca, Al, and Si. Ligands known to be effective in lanthanide/actinide separation were evaluated based on a series of criteria such as selectivity and association to organosilica through hydrophobicity. Batch experiments were conducted to establish the best conditions (e.g., pH, eluent, etc.) and best ligand systems for the effective extraction of REEs from the alkaline feed solution obtained from the hydrothermal leaching process. Once the organosilica-ligand extraction media was developed for REE concentration, an acidic solution was used to back extract and concentrate the REEs into a heavily REE-laden strip solution. The REEs in the strip solution were precipitated with oxalate to produce rare earth oxides.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

High manganese redox variability and manganate predominance in temperate soil profiles as determined by X-ray absorption spectroscopy

Manganese speciation is a key to understanding the fate of contaminants, nutrients, and organic matter in soils. To date, quantification of Mn species in bulk soils has been performed mainly by sequential extraction methods and rarely supported by spectroscopic analysis. In order to obtain quantitative information on the Mn species inventory of soils, we investigated 46 soil horizons (<2-mm fraction, 45.1–2,280 mg/kg Mn) of nine typical Central European soils (Cambisols, Chernozems, Luvisols, Podzol, Stagnosol) by chemical Mn analyses and Mn K-edge X-ray absorption spectroscopy, and related speciation results to major soil properties. Amounts of Mn 2+ , Mn 3+ , and Mn 4+ and the average oxidation state of Mn were evaluated by linear combination fitting (LCF) of X-ray absorption near edge structure (XANES) spectra. Additionally, we used extended X-ray absorption fine structure (EXAFS) spectroscopy to identify and quantify major Mn species. For this, EXAFS spectra of 20 organic and mineral soil samples from five soils (Cambisols, Chernozem, Luvisol) were analyzed by LCF and shell fitting. XANES analyses revealed a high Mn redox variability in organic surface layers, with Mn 2+ being most abundant (≤100%, $\overline{x}$ = 54%), followed by Mn 3+ (≤80%, $\overline{x}$ = 32%) and Mn 4+ (≤55%, $\overline{x}$ = 14%). Mineral soil horizons contained significantly less Mn 2+ (≤56%, $\overline{x}$ = 23%), about equal quantities of Mn 3+ (≤68%, $\overline{x}$ = 31%), and were enriched in Mn 4+ (≤89%, $\overline{x}$ = 46%). EXAFS analyses implied the presence of six major Mn species groups: manganates, organically complexed Mn, Mn(III) oxyhydroxides, silicate-bound Mn, Mn oxides without tunnel- or layer structure, and physisorbed Mn. In litter horizons, Mn was mainly present in organic complexes (58–91%, $\overline{x}$ = 78%) and as physisorbed Mn (≤15%), but individual horizons also comprised manganates, Mn(III) oxyhydroxides, and silicate-bound Mn. Manganates, likely mixtures of phyllomanganates with hexagonal layer symmetry and tectomanganates, dominated in all mineral soil horizons (37–94%, $\overline{x}$ = 67%). Correlation analysis showed that manganates dissolve completely during dithionite-citrate and acid ammonium oxalate extractions, and suggested that Mn 4+ -rich manganates preferentially form under less acidic soil conditions, partly by oxidation of organically complexed Mn(II), and that they are enriched in the soil clay fraction. Mineral soil horizons also contained minor quantities of organically complexed Mn (≤39%, $\overline{x}$ = 11%), silicate-bound Mn (≤30%, $\overline{x}$ = 8%), Mn(III) oxyhydroxides (≤37%, $\overline{x}$ = 7%), Mn oxides without tunnel- or layer structure (≤18%, $\overline{x}$ = 5%), and physisorbed Mn (≤14%, $\overline{x}$ <1%). The detection of Mn(III) oxyhydroxides such as feitknechtite (β-MnOOH) or groutite (α-MnOOH) as well as the spinel hausmannite (Mn 3 O 4 ) in acidic soils is remarkable, since their formation is normally linked to neutral or alkaline pH conditions. Minor contributions of silicate-bound Mn indicate the release of Mn from primary minerals already at early stages of soil formation, and low concentrations of physisorbed Mn suggest that exchangeable Mn is rapidly converted into manganates in oxic soils. In conclusion, the predominance of manganates in mineral soils has far-reaching implications for the functioning of soils and biogeochemical element cycles, as these minerals play an important role in metal binding, plant nutrition, and redox-related processes.

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

Ab Initio Studies of Discharge Mechanism of MnO 2 in Deep-Cycled Rechargeable Zn/MnO 2 Batteries

Rechargeable alkaline Zn/MnO 2 batteries are an attractive solution for large-scale energy storage applications. Recently, Bi and Cu additives have been used to increase the cycle life and capacity of rechargeable Zn/MnO 2 batteries, with an equivalent of the full two-electron capacity realized for many cycles, in the absence of zinc. However, the mechanism of the effect of Bi and Cu on the performance of rechargeable Zn/MnO 2 batteries has not been investigated in detail. We apply first-principles density functional computational methods to study the discharge mechanisms of the unmodified and Bi/Cu-modified γ -MnO 2 electrodes in rechargeable alkaline Zn/MnO 2 batteries. Using the results of our calculations, we analyze the possible redox reaction pathways in the γ -MnO 2 electrode and identify the electrochemical processes leading to the formation of irreversible discharge reaction products, such as hausmannite and hetaerolite. Our study demonstrates the possibility of formation of intermediate Bi-Mn and Cu-Mn oxides in deep-cycled Bi/Cu-modified MnO 2 electrodes. The formation of intermediate Bi-Mn and Cu-Mn oxides could reduce the rate of accumulation of irreversible reaction products in the MnO 2 electrode and improve the rechargeability and cyclability of Zn/MnO 2 batteries.

25 ENERGY STORAGE↗
NASA NTRS1997

Intracellular pH changes in human aortic smooth muscle cells in response to fluid shear stress

The smooth muscle cell (SMC) layers of human arteries may be exposed to blood flow after endothelium denudation, for example, following balloon angioplasty treatment. These SMCs are also constantly subjected to pressure driven transmural fluid flow. Flow-induced shear stress can alter SMC growth and metabolism. Signal transduction mechanisms involved in these flow effects on SMCs are still poorly understood. In this work, the hypothesis that shear stress alters the intracellular pH (pHi) of SMC is examined. When exposed to venous and arterial levels of shear stress, human aortic smooth muscle cells (hASMC) undergo alkalinization. The alkalinization plateau persisted even after 20 min of cell exposure to flow. Addition of amiloride (10 micromoles) or its 5-(N-ethyl-N-isopropyl) analog (EIPA, 10 micromoles), both Na+/H+ exchanger inhibitors, attenuated intracellular alkalinization, suggesting the involvement of the Na+/H+ exchanger in this response. The same concentrations of these inhibitors did not show an effect on pHi of hASMCs in static culture. 4-Acetamido-4'-isothio-cyanatostilbene-2,2'-disulfonic acid (SITS, 1 mM), a Cl-/HCO3- exchange inhibitor, affected the pHi of hASMCs both in static and flow conditions. Our results suggest that flow may perturb the Na+/H+ exchanger leading to an alkalinization of hASMCs, a different response from the flow-induced acidification seen with endothelial cells at the same levels of shear stress. Understanding the flow-induced signal transduction pathways in the vascular cells is of great importance in the tissue engineering of vascular grafts. In the case of SMCs, the involvement of pHi changes in nitric oxide production and proliferation regulation highlights further the significance of such studies.

NASA Discipline Cell Biology↗
DOE OSTI2022

Recycling of Lead Pastes from Spent Lead–Acid Batteries: Thermodynamic Constraints for Desulphurization

Lead–acid batteries are important to modern society because of their wide usage and low cost. The primary source for production of new lead–acid batteries is from recycling spent lead–acid batteries. In spent lead–acid batteries, lead is primarily present as lead pastes. In lead pastes, the dominant component is lead sulfate (PbSO 4 , mineral name anglesite) and lead oxide sulfate (PbO•PbSO 4 , mineral name lanarkite), which accounts for more than 60% of lead pastes. In the recycling process for lead–acid batteries, the desulphurization of lead sulfate is the key part to the overall process. In this work, the thermodynamic constraints for desulphurization via the hydrometallurgical route for recycling lead pastes are presented. The thermodynamic constraints are established according to the thermodynamic model that is applicable and important to recycling of lead pastes via hydrometallurgical routes in high ionic strength solutions that are expected to be in industrial processes. The thermodynamic database is based on the Pitzer equations for calculations of activity coefficients of aqueous species. The desulphurization of lead sulfates represented by PbSO 4 can be achieved through the following routes. (1) conversion to lead oxalate in oxalate-bearing solutions; (2) conversion to lead monoxide in alkaline solutions; and (3) conversion to lead carbonate in carbonate solutions. Among the above three routes, the conversion to lead oxalate is environmentally friendly and has a strong thermodynamic driving force. Oxalate-bearing solutions such as oxalic acid and potassium oxalate solutions will provide high activities of oxalate that are many orders of magnitude higher than those required for conversion of anglesite or lanarkite to lead oxalate, in accordance with the thermodynamic model established for the oxalate system. An additional advantage of the oxalate conversion route is that no additional reductant is needed to reduce lead dioxide to lead oxide or lead sulfate, as there is a strong thermodynamic force to convert lead dioxide directly to lead oxalate. As lanarkite is an important sulfate-bearing phase in lead pastes, this study evaluates the solubility constant for lanarkite regarding the following reaction, based on the solubility data, PbO•PbSO 4 + 2H + ⇌ 2Pb 2+ + SO 4 2– + H 2 O(l).

25 ENERGY STORAGE↗
DOE OSTI2023

Hydrogenated TiO 2 Carbon Support for PtRu Anode Catalyst in High‐Performance Anion‐Exchange Membrane Fuel Cells

Abstract The availability of durable, high‐performance electrocatalysts for the hydrogen oxidation reaction (HOR) is currently a constraint for anion‐exchange membrane fuel cells (AEMFCs). Herein, a rapid microwave‐assisted synthesis method is used to develop a core–shell catalyst support based on a hydrogenated TiO 2 /carbon for PtRu nanoparticles (NPs). The hydrogenated TiO 2 provides a strong metal‐support interaction with the PtRu NPs, which improves the catalyst's oxophilicity and HOR activity compared to commercial PtRu/C and enables greater size control of the catalyst NPs. The as‐synthesized PtRu/TiO 2 /C‐400 electrocatalyst exhibits respectable performance in an AEMFC operated at 80 °C, yielding the highest current density (up to 3× higher) within the catalytic region (compared at 0.80–0.90 V) and voltage efficiency (68%@ 0.5 A cm −2 ) values in the compared literature. In addition, the cell demonstrates promising short‐term voltage stability with a minor voltage decay of 1.5 mV h −1 . This “first‐of‐its‐kind in alkaline” work may open further research avenues to develop rapid synthesis methods to prepare advanced core–shell metal‐oxide/carbon supports for electrocatalysts for use in the next‐generation of AEMFCs with potential applicability to the broader electrochemical systems research community.

08 HYDROGEN↗
DOE OSTI2024

Unlocking High Capacity and Reversible Alkaline Iron Redox Using Silicate-Sodium Hydroxide Hybrid Electrolytes

Alkaline iron (Fe) batteries are attractive due to the high abundance, low cost, and multiple valent states of Fe but show limited columbic efficiency and storage capacity when forming electrochemically inert Fe 3 O 4 on discharging and parasitic H 2 on charging. Herein, sodium silicate is found to promote Fe(OH) 2 /FeOOH against Fe(OH) 2 /Fe 3 O 4 conversions. Electrochemical experiments, operando X-ray characterization, and atomistic simulations reveal that improved Fe(OH) 2 /FeOOH conversion originates from (i) strong interaction between sodium silicate and iron oxide and (ii) silicate-induced strengthening of hydrogen-bond networks in electrolytes that inhibits water transport. Furthermore, the silicate additive suppresses hydrogen evolution by impairing energetics of water dissociation and hydroxyl de-sorption on iron surfaces. In conclusion, this new silicate-assisted redox chemistry mitigates H 2 and Fe 3 O 4 formation, improving storage capacity (199 mAh g -1 in half-cells) and coulombic efficiency (94 % after 400 full-cell cycles), paving a path to realizing green battery systems built from earth-abundant materials.

36 MATERIALS SCIENCE↗
NASA NTRS1979

Effect of silicate ions on electrode overvoltage

The influence of the addition of a silicate to a caustic solution (KOH) is studied in order to determine the degree to which silicates inhibit the corrosion of chrysotile under conditions of electrolysis at working temperatures of 100 C and above. In an alkaline solution containing various silicate concentrations, current density was increased and electrode overvoltage was measured. Results show that silicate ion concentrations in the electrolyte increase with temperature without effecting electrochemical performance up to 115 C at 700 MA/sqcm. At this point the concentration is about 0.5 g Si/100 g KOH. Beyond this limit, electrolytic performance rapidly degenerates due to severe oxidation of the electrodes.

Gras, J. M.↗
DOE OSTI2020

A stable and highly selective metalloporphyrin based framework for the catalytic oxidation of cyclohexene

A new metalloporphyrin framework of molybdenum Mo 2 O 4 (C 48 H 28 N 4 O 8 )·(CH 3 ) 2 NH·5H 2 O·2DMF (Mo 2 TCPP) was synthesized from tetrakis(4-carboxyphenyl)porphyrin (H 4 TCPP) and sodium molybdate dihydrate by a hydrothermal method. Mo 2 TCPP is a 3D network with two sub-units, in which both TCPP ligands and each Mo 2 dimer act as four connection nodes. The crystal structure was determined by single crystal analysis and further characterized by FTIR, SEM, EDX, PXRD, XPS and TGA. Here cumene hydrogen peroxide and hydrogen peroxide were used as oxidants to study the catalytic activity of new metalloporphyrins in the oxidation of cyclohexene at different temperatures. The conversion rate of cyclohexene and the selectivity of epoxycyclohexane were both higher than 99%, which was better than the previously published research results. The stability of the catalyst before and after the reaction was further tested for 10 runs without obvious degradation. The catalyst was stable in different solutions such as acidic, water and alkaline. These results shed light on the future development of new catalytic materials based on metalloporphyrin.

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

Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions

Ultraviolet (UV) photolysis of nitrite ions (NO 2 – ) in aqueous solutions produces a suite of radicals, viz., NO · , O – , · OH, and · NO 2 . The O – and NO · radicals are initially formed from the dissociation of photoexcited NO 2 – . The O – radical undergoes reversible proton transfer with water to generate · OH. Both · OH and O – oxidize the NO 2 – to · NO 2 radicals. The reactions of · OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO · , · OH, and · NO 2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO 2 – solvation were determined to alter the initial yields of · NO and · OH radicals as well as alter the reactivity of NO 2 – toward · OH, impacting the production of · NO 2 . The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed.

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

Electronic interactions and stability issues at the copper-graphene interface in air and in alkaline solution under electrochemical control

A micro-electrochemical cell is sealed with a polymer-free single-layer graphene (SLG) membrane to monitor the stability of Cu nanoparticles (NPs) attached to SLG, as well as the interfacial electronic interactions between Cu NPs and SLG both in air and in a mildly alkaline aqueous solution under electrochemical control. A combination of techniques, including in-situ Kelvin probe force microscopy (KPFM) and ex-situ electron microscopy, are applied. When Cu NPs are metallic at cathodic potentials, there is a relatively bias-independent offset in the SLG work function due to charge transfer at the Cu-SLG contact. When Cu NPs are oxidized at anodic potentials, on the other hand, the work function of SLG also depends on the applied bias in a quasi-linear fashion due to electrochemical gating, in addition to charge transfer at the CuOx-SLG contact. Furthermore, Cu NPs were found to oxidize and detach from SLG when kept under anodic potentials for a few hours, whereas they remain adhered to SLG at cathodic potentials. This is attributed to water intercalation at the CuO-SLG interface associated with the enhanced hydrophilicity of positively polarized graphene, as supported by the absence of Cu detachment following oxidation by galvanic corrosion in air.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Facile synthesis of Co(OH)2 nanoneedle arrays grown on stainless steel for industrial electrochemical oxygen evolution reaction

The electrochemical oxygen evolution reaction (OER) is a critical half-reaction in a variety of energy conversion and storage applications, however, OER suffers from sluggish kinetics due to the four proton-electron transfer processes. To remedy this, interfacial engineering proves an effective strategy to design high active OER catalysts. Herein, we report a facile synthesis of Co(OH)2 nanoneedle (Co-NN) arrays grown on stainless steel (SS) via a one-step hydrothermal reaction, and the resultant impressive OER performance. Particularly, the Co-NN/SS needs 267, 307, and 576 mV overpotentials to reach 10, 100, and 1000 mA cm−2 in 1 M KOH & room temperature, and the overpotentials drop to 199, 257, and 283 mV to achieve the same current densities in 30 wt% KOH & 80 °C. Additionally, an alkaline water electrolysis (AWE) cell coupled with Co-NN/SS anode and PtRu/NiMo cathode only requires 1.65 and 1.73 V iR-free cell voltage to reach 1.0 and 2.0 A cm−2, respectively. The sterling OER performance could be attributed to four possible reasons, the Fe in SS surface tailoring the electronic properties of Co(OH)2, the mixed metal oxides on SS surface accelerating surface reconstruction of Co(OH)2 nanoneedles into CoOOH active species, a Ni-rich surface layer formation cooperatively boosting the OER activity, and a local electric field effect concentrating reactants on the tip surface and accelerating the mass transfer. This work provides a facile approach for synthesizing highly efficient OER catalysts for industrial applications by interfacial engineering.

Lyu, Xiang [ORNL] (ORCID:0000000208673248)↗
DOE OSTI2023

The effect of ferrous sulfate pretreatment on the optimal temperature for production of sugars during autothermal pyrolysis

Fast pyrolysis is a promising technology for producing cellulosic sugars from lignocellulosic biomass. Success in this endeavor requires measures that prevent naturally occurring alkali and alkaline earth metals (AAEM) from breaking pyranose and furanose rings in lignocellulosic biomass. This is especially critical for high ash feedstocks like corn stover and other kinds of herbaceous biomass. Pretreating corn stover with ferrous sulfate converts AAEM into thermally stable salts, which passivates the catalytic activity of these metals and dramatically improves sugar yields. AAEM passivation in combination with autothermal (partial oxidative) operation improves the prospects for intensifying the production of sugars via fast pyrolysis. We hypothesized that pretreated biomass pyrolyzed in the presence of oxygen can substantially influence the temperature dependence of pyrolysis kinetics. Here, we found that autothermal (air-blown) pyrolysis of ferrous sulfate pretreated corn stover achieved maximum sugar yield of 15.6 wt% (biomass basis) at 450 °C, whereas the maximum phenolic oil yield of 9.2 wt% (biomass basis) was reached at 500 °C. Considering these tradeoffs in yields of these highly desirable pyrolysis products, the ideal operating temperature is between 450 and 500 °C. These results suggest that two-stage pyrolysis might allow maximum recovery of both sugars and phenolic oil.

09 BIOMASS FUELS↗
DOE OSTI2021

Influences of pH and substrate supply on the ratio of iron to sulfate reduction

Iron reduction and sulfate reduction often occur simultaneously in anoxic systems, and where that is the case, the molar ratio between the reactions (i.e., Fe/SO 4 2- reduced) influences their impact on water quality and carbon storage. Previous research has shown that pH and the supply of electron donors and acceptors affect that ratio, but it is unclear how their influences compare and affect one another. This study examines impacts of pH and the supply of acetate, sulfate, and goethite on the ratio of iron to sulfate reduction in semi-continuous sediment bioreactors. We examined which parameter had the greatest impact on that ratio and whether the parameter influences depended on the state of each other. Results show that pH had a greater influence than acetate supply on the ratio of iron to sulfate reduction, and that the impact of acetate supply on the ratio depended on pH. In acidic reactors (pH 6.0 media), the ratio of iron to sulfate reduction decreased from 3:1 to 2:1 as acetate supply increased (0-1 mM). In alkaline reactors (pH 7.5 media), iron and sulfate were reduced in equal proportions, regardless of acetate supply. Secondly, a comparison of experiments with and without sulfate shows that the extent of iron reduction was greater if sulfate reduction was occurring and that the effect was larger in alkaline reactors than acidic reactors. Thus, the influence of sulfate supply on iron reduction extent also depended on pH and suggests that iron reduction grows more dependent on sulfate reduction as pH increases. Our results compare well to trends in groundwater geochemistry and provide further evidence that pH is a major control on iron and sulfate reduction in systems with crystalline (oxyhydr)oxides. pH not only affects the ratio between the reactions but also the influences of other parameters on that ratio.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1992

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

The objective was to identify promising electrocatalyst/support systems for oxygen cathodes capable of operating at ultrahigh current densities in alkaline fuel cells. Such cells will require operation at relatively high temperatures and O2 pressures. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, lithiated NiO and La-Ni perovskites. Several of these materials were prepared using techniques that had not been previously used to prepare them. Particularly interesting was the use of the alkaline solution technique to prepare Pt-doped and Pb-Ru pyrochlores in high area form. Also interesting was the use of the fusion (melt) method for preparing the Pb-Ru pyrochlore. Several of the materials were also deposited with platinum. Well-crystallized Pb2Ru2O(7-y) was used to fabricate very high performance O2 cathodes with good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approx. 140 C in concentrated KOH. For some of the samples, fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. Pyrochlores that were not well-crystallized were found to be unstable in alkaline solution. Very good O2 reduction performance and stability were observed with Pb2RuO(7-y) in a carbon-based gas-fed electrode with an anion-conducting membrane placed on the electrolyte side of the electrode. The performance came within a factor of about two of that observed without carbon. High area platinum and gold supported on several conductive metal oxide supports were examined. Only small improvements in O2 reduction performance at room temperature were observed for Pb2Ru2O(7-y) as a support because of the high intrinsic activity of the pyrochlore. In contrast, a large improvement was observed for Li-doped NiO as a support for Pt. Very poor performance was observed for Au deposited on Li-NiO at approx. 150 C. Nearly reversible behavior was observed for the O2/OH(-) couple for Li-doped NiO at approx. 200 C. The temperature dependence for the O2 reduction was examined.

Tryk, Donald A.↗
NASA NTRS1997

Fossilization of Coniform (Phormidium) Stromatolites In Siliceous Thermal Springs, Yellowstone National Park

We have studied fossilization processes in well-developed cyanobacterial mats present in mid-terrace ponds of silica-precipitating thermal springs of Yellowstone National Park. These mats occur over temperatures of approx.35-60 C and are dominated by species of Phormidium. Within Bonded systems two end member environments have been distinguished based temperature, depth, and the stability of spring inflows, each differing substantially in the style of stromatolite morphogenesis and fossilization. Type 1 systems include shallow, ephemeral ponds where water flow and temperature fluctuates widely on a seasonal basis; mats typically secrete rapidly up to the air-water interface, forming exposed islands. Silicification occurs primarily by the wicking of water onto the surface of exposed mats, leading to the evaporative concentration of silica near the surface. pH microelectronic measurements in partially-exposed columns show strong gradients in pH with values exceeding 10.5 in the upper am of silicifying mats, decreasing to <9.0 a few mm below the surface. High oxygen concentrations lead to the rapid oxidation of most organic materials. In Type I systems, the tops of coniform and columnar stromatolites become silicified first, followed by the bases. This typically leads to extensive fragmentation during the initial stages of burial. Case 2 systems include deeper ponds where the water flow, temperature and depth are seasonally more stable, and where mats develop larger-scale tufts and columns. Alkalinity in permanently submerged mats increases into tuft interiors from approx.9.0 near the surface to >10.0 at depth. Moderate silicification is apparent throughout mat frameworks, although there is frequently a densely silicified core near the base. In Type 2 systems, preservation of the coniform and columnar architecture of stromatoilites is much more robust. Sub-fossil examples suggest minimal fragmentation prior to burial. Comparative rapid analysis of the phone zones of submerged and exposed (silicifying) mats demonstrated the recovery of comparable levels of esterified fatty acids in both types of mats. Membrane lipids apparently remain intact during the early stages of silicification, although their fate during early diagenesis is still being evaluated.

Farmer, Jack↗
NASA NTRSDate not supplied

Identifying Sources of Sulfate Preserved in High Elevation Lava Tubes From Mauna Loa, Hawaii

Volcanic sulfates record a history of their formation pathways in their triple oxygen isotope compositions, making them a powerful target for understanding atmospheric chemistry. To understand how these isotopic signals may be preserved in sulfate minerals, we investigate multiple O and S isotopes of thenardite, mirabilite, and gypsum from in a Mars analog environment: a pair of lava tubes near the summit of Mauna Loa, Hawaii. Based on 16 O-, 17 O- 18 O compositions, the primary oxygen sources for sulfates in the lava tube are atmospheric oxygen (O 2 ), peroxide (H 2 O 2 ), and ozone (O 3 ). We suggest the isotopic signature of O 2 originates from combustion of reduced sulfur gases and/or elemental sulfur at the eruptive source or within the lava tube soon after skylight collapse. Sulfate with isotopic signatures of peroxide and ozone are typically expected from aqueous reactions in cloud droplets. Chemical modeling indicates the observed proportion of ozone sourced sulfate requires pH greater than ~5.4, higher than measured cloud water pH, instead suggesting the observed O 3 signature could not have formed in cloud water droplets. We interpret that sulfate possessing an ozone signature in the lava tube sulfates formed on wetted surfaces of the lava tubes with alkalinity from alteration of basaltic glass. Furthermore, the oxygen and sulfur isotopes of the sulfate are uncorrelated. Multiple sulfur isotopes ( 32 S- 33 S- 34 S- 36 S) from the Mauna Loa sulfates are consistent with ocean island basalt from Pitcairn, suggesting the sulfate-sulfur has not been modified compared to its volcanic source. The findings of this study indicate that oxidation by ozone plays a key role in the formation of sulfate within lava tubes. We also find that combustion is a significant pathway toward sulfuric acid formation in volcanic environments. Similar signatures should be expected on other planets if volcanism is a significant sulfate source, as has been suggested for Mars. If true, sulfates in returned samples from Mars may hold key information on pO 2 , pCO 2 and planetary scale oxygen fluxes at the time of sulfate formation.

Justin Hayles↗