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Atomistic mechanisms for catalytic transformations of NO to NH3, N2O, and N2 by Pd

The industrial pollutant NO is a potential threat to the environment and to human health. Thus, selective catalytic reduction of NO into harmless N2, NH3, and/or N2O gas is of great interest. Among many catalysts, metal Pd has been demonstrated to be most efficient for selectivity of reducing NO to N2. However, the reduction mechanism of NO on Pd, especially the route of N−N bond formation, remains unclear, impeding the development of new, improved catalysts. We report here the elementary reaction steps in the reaction pathway of reducing NO to NH3, N2O, and N2, based on density functional theory (DFT)-based quantum mechanics calculations. We show that the formation of N2O proceeds through an Eley-Rideal (E−R) reaction pathway that couples one adsorbed NO* with one non−adsorbed NO from the solvent or gas phase. This reaction requires high NO* surface coverage, leading first to the formation of the trans-(NO)2* intermediate with a low N−N coupling barrier (0.58 eV). Notably, trans-(NO)2* will continue to react with NO in the solvent to form N2O, that has not been reported. With the consumption of NO and the formation of N2O* in the solvent, the Langmuir-Hinshelwood (L-H) mechanism will dominate at this time, and N2O* will be reduced by hydrogenation at a low chemical barrier (0.42 eV) to form N2. In contrast, NH3 is completely formed by the L-H reaction, which has a higher chemical barrier (0.87 eV). Our predicted E-R reaction has not previously been reported, but it explains some existing experimental observations. In addition, we examine how catalyst activity might be improved by doping a single metal atom (M) at the NO* adsorption site to form M/Pd and show its influence on the barrier for forming the N−N bond to provide control over the product distribution.

Physics↗

Latitudinal changes of composition in the disturbed thermosphere from Esro 4 measurements

Densities of N2, O, Ar, and He at a height of 280 km, obtained from gas analyzer measurements aboard Esro-4, were analyzed to establish a global pattern for variations that are associated with geomagnetically induced disturbances. It is shown that during longer periods of sustained geomagnetic activity, thermospheric temperature increases with geomagnetic latitude, reaching a maximum in the region of the magnetic pole, while during short-lived magnetic storms, the maximum temperature may be reached in the auroral zones. The observed variations of composition in middle and high latitudes can be explained by assuming that temperature variations are accompanied by variations in the height of the homopause. In the equatorial region the four gases studied vary in phase with similar amplitudes during a magnetic storm, indicating a density wave proceeding from higher latitudes.

Jacchia, L. G.↗

Controlled ecological life support systems; Proceedings of Workshop II of the 26th COSPAR Plenary Meeting, Toulouse, France, June 30-July 11, 1986

The present conference on the development status of Controlled Ecological Life Support Systems (CELSSs) discusses food production and gas exchange with the Spirulina blue-green alga, biomass recycling for greater energy efficiency in algal culture CELSSs, algal proteins for food processing in a CELSS, a CELSS with photosynthetic N2-fixing cyanobacteria, the NASA CELSS program, and vapor compression ditillation and membrane technology for water revitalization. Also discussed are a fundamental study of CELSS gas monitoring, the application of catalytic wet oxidation to CELSS, a large-scale perspective on ecosystems, Japanese CELSS research activities, the use of potatoes in bioregenerative life-support, wheat production in controlled environments, and a trickle water and feeding system in plant culture.

Macelroy, R. D.↗

Study of dynamics of minor constituents in the thermosphere

The global distribution of helium and argon in the terrestrial thermosphere is described. It is based on the extension of a three-dimensional single-fluid numerical model of the thermosphere previously developed by the authors to treat the dynamics of a minor gas imbedded in a background gas made up of N2, O2, and O. Empirical models of the upper atmosphere, based on satellite drag and mass spectrometer data, are used to specify the background gas density and temperature as functions of altitude, latitude, and local time for a given day of the year. Effects of solar activity, eddy diffusion, and exospheric transport on the global distribution of minor gases are investigated.

Straus, J. M.↗

Dissociation of diatomic gases

The Landau-Zener theory of reactive cross sections has been applied to diatomic molecules dissociating from a ladder of rotational and vibrational states. Although the preexponential factor of the Arrhenius rate expression is shown to be a complex function of the dimensionless activation energy, the average over all states in the ladder is well represented by a single factor that varies about as T exp (-n), where the coefficient n is the order of unity. This relation agrees very well with experimental data for dissociation of O2 and N2, for example. The results validate previous empirical assignment of a single preexponential factor in the Arrhenius expression and justify the extrapolation of the expression well beyond the range of data. The theory is then used to calculate the effect of vibrational nonequilibrium on dissociation rate. For Morse oscillators the results are about the same as for harmonic oscillators, and the dissociation from a ladder of equilibrium rotational and nonequilibrium vibrational states is close to an analytic approximation provided by Hammerling, Kivel, and Teare for harmonic oscillators all dissociating from the ground rotational state.

Hansen, C. F.↗

The Mars Project: Avoiding Decompression Sickness on a Distant Planet

A cost-effective approach for Mars exploration is to use available resources, such as water and atmospheric gases. Nitrogen (N2) and argon (Ar) are available and could form the inert gas component of a habitat atmosphere at 8.0, 9.0, or 10.0 pounds per square inch (psia). The habitat and space suit are designed as an integrated system: a comfortable living environment about 85% of the time and a safe working environment about 15% of the time. A goal is to provide a system that permits unrestricted exploration of Mars, but the risk of decompression sickness (DCS) during the extravehicular activity in a 3.75-psia suit, after exposure to any of the three habitat conditions, may limit unrestricted exploration. I evaluate here the risk of DCS since a significant proportion of a trinary breathing gas in the habitat might contain Ar. I draw on past experience and published information to extrapolate into untested, multivariable conditions to evaluate risk. A rigorous assessment of risk as a probability of DCS for each habitat condition is not yet possible. Based on many assumptions about Ar in hypobaric decompressions, I conclude that the presence of Ar significantly increases the risk of DCS. The risk is significant even with the best habitat option: 2.56 psia oxygen, 3.41 psia N2, and 2.20 psia Ar. Several hours of prebreathing 100% 02, a higher suit pressure, or a combination of other important variables such as limited exposure time on the surface or exercise during prebreathe would be necessary to reduce the risk of DCS to an acceptable level. The acceptable level for DCS risk on Mars has not yet been determined. Mars is a great distance from Earth and therefore from primary medical care. The acceptable risk would necessarily be defined by the capability to treat DCS in the Rover vehicle, in the habitat, or both.

Conkin, Johnny↗

Ammonia Leak Locator Study

The thermal control system of International Space Station Alpha will use liquid ammonia as the heat exchange fluid. It is expected that small leaks (of the order perhaps of one pound of ammonia per day) may develop in the lines transporting the ammonia to the various facilities as well as in the heat exchange equipment. Such leaks must be detected and located before the supply of ammonia becomes critically low. For that reason, NASA-JSC has a program underway to evaluate instruments that can detect and locate ultra-small concentrations of ammonia in a high vacuum environment. To be useful, the instrument must be portable and small enough that an astronaut can easily handle it during extravehicular activity. An additional complication in the design of the instrument is that the environment immediately surrounding ISSA will contain small concentrations of many other gases from venting of onboard experiments as well as from other kinds of leaks. These other vapors include water, cabin air, CO2, CO, argon, N2, and ethylene glycol. Altogether, this local environment might have a pressure of the order of 10(exp -7) to 10(exp -6) torr. Southwest Research Institute (SwRI) was contracted by NASA-JSC to provide support to NASA-JSC and its prime contractors in evaluating ammonia-location instruments and to make a preliminary trade study of the advantages and limitations of potential instruments. The present effort builds upon an earlier SwRI study to evaluate ammonia leak detection instruments [Jolly and Deffenbaugh]. The objectives of the present effort include: (1) Estimate the characteristics of representative ammonia leaks; (2) Evaluate the baseline instrument in the light of the estimated ammonia leak characteristics; (3) Propose alternative instrument concepts; and (4) Conduct a trade study of the proposed alternative concepts and recommend promising instruments. The baseline leak-location instrument selected by NASA-JSC was an ion gauge.

Dodge, Franklin T.↗

Method of Synthesizing a Novel Absorbent Titanosilicate Material (UPRM-5)

A titanium silicate variant named UPRM-5 was prepared using tetraethylammonium hydroxide as a structure-directing agent (SDA). Successful detemplation was achieved via ion exchange with NH4Cl. Effective functionalization was obtained after ion exchanging the detemplated material using SrCl2 and BaCl2. Adsorption of CO2 at 25 deg C in Sr(-) and Ba-UPRM-5 materials activated at different temperatures. For low partial pressures, the observed CO2 adsorption capacities increased as follows: NH4-UPRM-5 less than Sr-UPRM-5 less than Ba-UPRM-5. Both the Sr(-) and Ba-UPRM-5 materials exhibited outstanding selectivity for CO2 over CH4, N2 and O2.

Hernandez-Maldonado, Arturo↗

Fifteen-minute Extravehicular Activity Prebreathe Protocol Using NASA's Exploration Atmosphere (8.2 psia/ 34% 02)

A TBDM DCS probability model based on an existing biophysical model of inert gas bubble growth provides significant prediction and goodness-of-fit with 84 cases of DCS in 668 human altitude exposures. 2. Model predictions suggest that 15-minute O2 prebreathe protocols used in conjunction with suit ports and an 8.2 psi, 34% O2, 66% N2 atmosphere may enable rapid EVA capability for future exploration missions with the risk of DCS ≤ 12%.  EVA could begin immediately at 6.0 psi, with crewmembers decreasing suit pressure to 4.3 psi after completing the 15-minute in-suit prebreathe. 3. Model predictions suggest that intermittent recompression during exploration EVA may reduce decompression stress by 1.8% to 2.3% for 6 hours of total EVA time. Savings in gas consumables and crew time may be accumulated by abbreviating the EVA suit N2 purge to 2 minutes (20% N2) compared with 8 minutes (5% N2) at the expense of an increase in estimated decompression risk of up to 2.4% for an 8-hour EVA.  Increased DCS risk could be offset by IR or by spending additional time at 6 psi at the beginning of the EVA.  Savings of 0.48 lb of gas and 6 minutes per person per EVA corresponds to more than 31 hours of crew time and 1800 lb of gas and tankage under the Constellation lunar architecture. 6. Further research is needed to characterize and optimize breathing mixtures and intermittent recompression across the range of environments and operational conditions in which astronauts will live and work during future exploration missions. 7. Development of exploration prebreathe protocols will begin with definition of acceptable risk, followed by development of protocols based on models such as ours, and, ultimately, validation of protocols through ground trials before operational implementation.

Abercromby, Andrew F. J.↗

Plasma Activated Water for Crewed Transit and Planetary Habitation: A Study of Gas Type, Electrode Material, and Power Supply Selection and the Impact on the Final Frontier - FY21 CIF

An in-depth study of plasma activated water (PAW) generation was conducted to link changes in power supply, electrode material, input gas, and treatment time to the resulting reaction chemistry. These changes in chemistry can help tailor PAW for different space applications. An AC, DC, and nanosecond (ns) pulsed power supply were each used to generate PAW with stainless steel, copper, tungsten, or platinum (Pt) electrodes while utilizing air, nitrogen (N2), carbon dioxide (CO2), helium (He), or argon (Ar) as the feed gas. Tap or deionized (DI) water was treated for 1 to 15 minutes, and the generated PAW was tested for changes in pH, conductivity, oxidation reduction potential, nitrates (NO3-), ammonium (NH4+), and peroxide. Calculations showed that the production of reactive nitrogen species was the leading cause of pH and conductivity changes. The DC generated air plasma was able to reduce the pH of DI water and generate NO3‑. The pulsed supply, operating at 20% of the input power of the DC supply, lowered the pH generated NO3‑. When a simulated Martian gas mixture of 95% CO2 and 5% N2 was used as the feed gas, NO3‑ was generated with the DC and pulsed supplies, respectively. Mixing PAW with plasma generated ash from inedible biomass allowed pH control, thus enhancing PAW’s potential use for sanitation applications. The large shift in pH was used to study sanitation effects of Escherichia coli (E. coli) reduction and Staphylococcus aureus (S. aureus), in which log reductions were found to be negligible. Additionally, the plasma generated ash in combination with PAW was also implemented in 10-day microgreen growth trials, in which PAW and ash resulted in quicker emergence of the microgreens compared to the standard growth conditions and comparable dry masses to Hoagland’s nutrient solution treated samples.

plasma activated water (PAW)↗

Development, Validation and Approval of A Planetary Extravehicular Activity Prebreathe Protocol: NASA Exploration Atmosphere Tests 1 & 2

INTRODUCTION: Denitrogenation prebreathe protocols used to mitigate DCS risk for Space Shuttle and International Space Station EVAs are validated for the microgravity environment, but the significantly increased risk of DCS during equivalent ambulatory surface EVAs make these protocols inapplicable to planetary/Lunar missions as planned by the Artemis program. Living in an “Exploration Atmosphere” of 56.5 kPa (8.2 psia), 34% O2, 66% N2 has been recommended by NASA for future Moon and Mars missions as a compromise that balances pre-EVA prebreathe duration, hypoxia, and flammability risk, assuming a 29.6 kPa (4.3 psi) spacesuit. A prebreathe validation campaign at NASA’s Johnson Space Center in 2022–2023 has aimed to validate the prebreathe durations and is being operationalized by NASA for use in upcoming Lunar EVAs. METHODS: Twelve volunteers lived in a hyboparic chamber for 11 days with an “exploration atmosphere” of 56.6kPa/34% O2 66% N2. Subjects acclimated to this atmosphere for 48 hrs and thereafter participated in five 6-hour simulated EVAs at 34kPa/85% O2 / 15% N2 over the course of 11 days. Prior to each simulated EVA, subjects underwent a 20-minute prebreathe at 85% O2. The EVA simulation was designed to include tasks that are physically and ergonomically representative of future planetary EVAs, proportionate to the subject’s VO2max. Decompression stress was evaluated during the simulated EVA by serial doppler and echocardiographs alternating every 15 min, as well as clinical monitoring for DCS signs/symptoms. Venous gas emboli (VGE) and DCS outcomes were verified against NASA Standard 3001, which guides allowable prebreathe protocol acceptance criteria. RESULTS AND DISCUSSION: Venous gas emboli (VGE) were identified during EVAs. No Grade IV VGE were observed. Two cases of mild, Type I DCS were identified in the subjects over the course of 50 EVA exposures. Ten planned EVA exposures were eliminated due to mask fit, metabolic rate, or subject safety concerns. One subject was removed from the study due to presence of left ventricular VGE. Additionally, two doppler techs also experienced DCS, and one case of hypoxia was noted. All cases of DCS resolved with treatment. No cases of severe DCS were observed. The observed incidence (4%, 1.1–13.5% at 95% confidence) met the NASA Standard 3001 criteria leading to the transition of this protocol from research to operational use for upcoming Lunar missions.

Exploration Atmosphere↗

Recent studies of the ocean nitrogen cycle

The nitrogen cycle in the ocean is dominated by the activities of organisms. External nitrogen inputs from land and from the atmosphere are small compared with rates of consumption and production by organisms and with rates of internal rearrangements of nitrogen pools within the ocean. The chief reservoirs of nitrogen are, in decreasing order of size: nitrogen in sediments, dissolved N2, nitrate, dissolved organic nitrogen (DON), particulate organic nitrogen (PON) (mostly organisms and their by-products). The biogenic fluxes of nitrogen were reviewed. The rate of PON decomposition in the surface layer must be comparable to the rate of ammonium consumption; and at the same time the nitrate consumption rate will be similar to the rates of: (1) sinking of PON out of the surface layer and its decompositon at depth, (2) the rate of nitrification at depth, and (3) the rate of nitrate return to the surface layer by upwelling.

Eppley, R. W.↗

Use of Intermittent Recompression and Nitrox Breathing Mixtures during Lunar Extravehicular Activities

INTRODUCTION: NASA's plans for lunar surface exploration include pressurized suitport rovers that are quickly ingressed and egressed with minimal consumables losses. This capability enables crewmembers to perform multiple short extravehicular activities (EVAs) at different locations in a single day versus a single 8-hr EVA. Modeling work and empirical human and animal data indicate that intermittent recompressions between EVA suit pressure and cabin pressure reduce decompression stress. Savings in crew time and gas losses may also be achieved if the N2 purge is shortened to 2 minutes, achieving 80% O2 (vs. 8 minutes, 95% O2). METHODS: A validated Tissue Bubble Dynamics Model was used to predict decompression stress using 80% and 95% O2 breathing mixtures during 3 x 2-hr EVAs (4.3 PSIA) with 1hr recompressions back to 8.0 PSIA (32% O2) versus a single 8-hr EVA. 15 minutes was spent at 6.0 PSIA before depressurizations to 4.3 PSIA; initial EVA tasks could be performed during this time. Model validation was based on significant prediction (p<0.001) and goodness of fit with 84 cases of DCS in 668 altitude exposures (McFadden s rho-squared=0.214). RESULTS: A 2.2% predicted increase in DCS risk due to the shortened purge is more than compensated for by a predicted 2.5% reduction in DCS risk due to intermittent recompression. 15 minutes at 80% O2, 6.0 PSIA prior to a 4.3 PSIA EVA prevents supersaturation in the brain and spinal cord (5-10 minute half-time compartments) and reduces tissue tensions in 40 min compartments, where most of the body s inert gas is located, to approximately the same levels (4.39 vs 4.00 PSIA) as achieved during a 40 min 95% O2 prebreathe at 10.2 PSIA. CONCLUSIONS: Intermittent recompressions between lunar EVAs may enable reductions in suit purge and prebreathe requirements, decompression stress, and/or suit operating pressures.

Gernhardt, M.L.↗

Role of electron pathway in dimensionally increasing water splitting reaction sites in liquid electrolytes

Hydrogen from water splitting is one of the most promising alternatives for fossil fuels in solving the global energy crisis, while its electrochemical reaction mechanism, especially in liquid electrolytes, remains unclear. Herein, how the electrode conductivity affects the reaction sites of oxygen evolution reactions (OERs) in acidic and alkaline solutions was investigated by employing visualization system and electrochemical testing. Inserting Au nanolayers greatly increased electrode conductivities, improved OER kinetics and reduced cell ohmic resistance, leading to excellent water splitting performances in both acidic and alkaline electrolytes. Furthermore, the in-situ visualization results showed more reaction sites and higher catalyst utilizations were achieved by augmenting the electrode conductivity, and reaction sites increased from 1-dimension to 2-dimension. Additionally, it was discovered that electrical conductivities of acidic and alkaline solutions are insufficient to overcome the sharp drop of potential in the electrical double layer for activating OER uniformly on low-conductivity catalysts, indicating the importance of electrical conductivity of the electrode in acidic and alkaline water electrolyzers. This study provided a guidance on how to develop efficient and compact electrodes for acidic and alkaline water electrolyzer stacks and other electrochemical devices, such as fuel cell, N2 reduction, CO 2 conversion, etc.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure sensitivity of ammonia electro-oxidation on transition metal surfaces: A first-principles study

Ammonia electro-oxidation is a promising catalytic reaction for application in alkaline fuel cells. In this paper we study the trends in this reaction on the (1 0 0) facet of eight fcc transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh. We calculate from first-principles (DFT-GGA-PW91) the energetics for two mechanisms: (i) the N + N mechanism and (ii) the Gerischer-Mauerer mechanism. The onset potentials for both mechanisms are provided for both (1 0 0) and (1 1 1) facets. We also calculate the activation energies for the N-N bond-making non-Faradaic events on Cu, Pt, Pd, Ni, Ir, and Rh. We discover that N* – which is considered a poison for Pt(1 1 1) – is a reactive intermediate on Pt(1 0 0), allowing for a facile dimerization to N2 on Pt(1 0 0) at high potentials. We draw similar analyses for the structure sensitivity on the other metals, and we conclude with some general principles to guide catalyst design for this reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Composition changes and empirical models

Empirical model descriptions of the response of the neutral thermosphere to magnetic activity have become increasingly sophisticated over the last two decades. The latest CIRA model (MSIS-86) includes a dependence of the thermospheric response to magnetic activity on altitude, latitude, local time, season, longitude, UT, and time history of magnetic activity. A primary assumption is that density changes are directly related to the measured magnetic activity and the goal is for the model to be representative of the typical or average response for any given level of magnetic activity under specified ancillary conditions. Unfortunately, available measurements for the larger storms are too sparse to give good averages and storm response may not be uniquely represented by current magnetic indices. Point by point comparisons with the MSIS-86 model have standard deviations of 20 percent for 0 and 30 percent for N2 and He at high latitudes during storm conditions.

Hedin, A. E.↗

Initiation and elongation of lateral roots in Lactuca sativa

Lactuca sativa cv. Baijianye seedlings do not normally produce lateral roots, but removal of the root tip or application of auxin, especially indole-butyric acid, triggered the formation of lateral roots. Primordia initiated within 9 h and were fully developed after 24 h by activating the pericycle cells opposite the xylem pole. The pericycle cells divided asymmetrically into short and long cells. The short cells divided further to form primordia. The effect of root tip removal and auxin application was reversed by 6-benzylaminopurine at concentrations >10(-8) M. The cytokinin oxidase inhibitor N1-(2chloro4pyridyl)-N2-phenylurea also suppressed auxin-induced lateral rooting. The elongation of primary roots was promoted by L-alpha-(2-aminoethoxyvinyl) glycine and silver ions, but only the latter enhanced elongation of lateral roots. The data indicate that the induction of lateral roots is controlled by basipetally moving cytokinin and acropetally moving auxin. Lateral roots appear to not produce ethylene.

NASA Discipline Plant Biology↗

Photochemistry of Triton's Atmosphere and Ionosphere

The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(exp -4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/sq cm/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/sq cm/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/sq cm/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(exp 3)sq cm/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8)x IO(exp 11)/cu cm. Chemistry above 200 km is driven by the solar EUV radiation (lambda less than 1000 A) and by precipitation of magnetospheric electrons with a total energy input of 10(exp 8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, 0, and C. They escape with the total rates of 7.7 x 10(exp 24)/ s, 4.5 x 10(exp 25)/s, 2.4 x 10(exp 25)/s, 4.4 x 10(exp 22)/s, and 1.1 x 10(exp 24), respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Ionospheric chemistry explains the formation of an E region at 150-240 km with HCO(+) as a major ion, and of an F region above 240 km with a peak at 320 km and C(+) as a major ion. The ionosphere above 500 km consists of almost equal densities of C(+) and N(+) ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there are four basic unknown values which have strong impacts on the composition and structure of the atmosphere and ionosphere. These values and their plausible ranges are the CO mixing ratio f(sub co) = 10(exp -4) - 10(exp -3), the magnetospheric electron energy input (1 +/- 0.5) x 10(exp 8) W, the rate coefficient of charge-exchange reaction N2(+) + C(kappa) = 10(exp -11) - 10(exp -10)cu cm/s, and the ion escape velocity upsilon(sub i) approx. equals 150 cm/s.

Krasnopolsky, Vladimir A.↗