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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Elimination of NO Pollutant in Semi-enclosed Spaces over Sodium-promoted Cobalt Oxyhydroxide (CoOOH) by Oxidation and Adsorption Mechanism

Low concentrations of NOx accumulated in air in semi-enclosed spaces is a severe health hazard, but its efficient removal at low cost is a grand challenge. A simple method in preparing CoOOH for low-concentration NO removal at room temperature is described here. The samples are synthesized by oxidizing Co(OH)2 to CoOOH with different oxidants (Na2S2O8, O2 and H2O2). Among them, CoOOH prepared by Na2S2O8 (Co-NS) shows remarkable performance for NO abatement, while the samples synthesized by and H2O2 (Co-HO) and O2 (Co-OG) have no apparent NO removal capacity. It is found that the Co-NS material contains a higher concentration of residual Na, which contributes to the decreased crystallinity and increased concentrations of surface active species (Co2+, active oxygen) for NO storage. Following NO storage, the material can be readily regenerated by water washing. The authors from East China University of Science and Technology acknowledge support from National Basic Research Program of China (2013CB933200), National Natural Science Foundation of China (21577035, 21577034), Commission of Science and Technology of Shanghai Municipality (15DZ1205305) and 111 Project (B08021). Aiyong Wang acknowledges the China Scholarship Council for the Joint-Training Scholarship Program with the Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the US DOE under contract DE-AC05-76RL01830. FG is supported by the U.S. DOE/Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office.

NOx abatement, NOx adsorber, ambient temperature, ↗
NASA NTRS2005

Bifunctional catalytic electrode

The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

Cisar, Alan↗
DOE OSTI2025

The Role of Cu 3+ in the Oxygen Evolution Activity of Copper Oxides

Cu-based oxides and hydroxides represent an important class of materials from a catalytic and corrosion perspective. In this study, we investigate the formation of bulk and surface Cu 3+ species that are stable under water oxidation catalysis in alkaline media. So far, no direct evidence existed for the presence of hydroxides (CuOOH) or oxides, which were primarily proposed by theory. Here, this work directly places CuOOH in the oxygen evolution reaction (OER) Pourbaix stability region with a calculated free energy of −208.68 kJ/mol, necessitating a revision of known Cu–H 2 O phase diagrams. We also predict that the active sites of CuOOH for the OER are consistent with a bridge O* site between the two Cu 3+ atoms with onset at ≥1.6 V vs the reversible hydrogen electrode (RHE), aligning with experimentally observed Cu 2+/3+ oxidation waves in cyclic voltammetry of Fe-free and Fe-spiked copper in alkaline media. Trace amounts of Fe (2 μg/mL (ppm) to 5 μg/mL) in the solution measurably enhance the catalytic activity of the OER, likely due to the adsorption of Fe species that serve as the active sites . Importantly, modulation excitation X-ray absorption spectroscopy (ME-XAS) of a Cu thin-film electrode shows a distinct Cu 3+ fingerprint under OER conditions at 1.8 V vs RHE. Additionally, in situ Raman spectroscopy of polycrystalline Cu in 0.1 mol/L (M) KOH revealed features consistent with those calculated for CuOOH in addition to CuO. Overall, this work provides direct evidence of bulk electrochemical Cu 3+ species under OER conditions and expands our longstanding understanding of the oxidation mechanism and catalytic activity of copper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

A Water Rich Mars Surface Mission Scenario

The surface of Mars once had abundant water flowing on its surface, but now there is a general perception that this surface is completely dry. Several lines of research have shown that there are sources of potentially large quantities of water at many locations on the surface, including regions considered as candidates for future human missions. Traditionally, system designs for these human missions are constrained to tightly recycle water and oxygen, and current resource utilization strategies involve ascent vehicle oxidizer production only. But the assumption of relatively abundant extant water may change this. Several scenarios were constructed to evaluate water requirements for human Mars expeditions to assess the impact to system design if locally produced water is available. Specifically, we have assessed water resources needed for 1) ascent vehicle oxidizer and fuel production, 2) open-loop water and oxygen life support requirements along with more robust usage scenarios, and 3) crew radiation protection augmentation. In this assessment, production techniques and the associated chemistry to transform Martian water and atmosphere into these useful commodities are identified, but production mass and power requirements are left to future analyses. The figure below illustrates the type of water need assessment performed and that will be discussed. There have been several sources of feedstock material discussed in recent literature that could be used to produce these quantities of water. This paper will focus on Mars surface features that resemble glacier-like forms on Earth. Several lines of evidence indicate that some of these features are in fact buried ice, likely remnants from an earlier ice age on Mars. This paper examines techniques and hardware systems used in the polar regions of Earth to access this buried ice and withdraw water from it. These techniques and systems will be described to illustrate options available. A technique known as a Rodriguez Well is assessed as a likely method for extracting water from these bodies of ice. The figure below is a sample of results from this assessment that will be discussed.

Hoffman, Stephen↗
NASA NTRSDate not supplied

Overview of NASA ISRU Plans, Priorites, and Activities

Introduction:The National Aeronautics andSpace Administration (NASA) of the United States ofAmerica (US) has initiated the Artemis Moon to Marsprogram to send astronauts (the first woman andperson of color) back to the lunar surface, create asustainable human lunar exploration program, andlead the first human exploration mission to the Marssurface in the 2030’s [1]. A major objective of thisprogram is to characterize the resources that exist onthe Moon and Mars, and learn how to utilize them forsustained and affordable exploration. Commonlyknown as In Situ Resource Utilization (ISRU), thesearch for, acquisition, and processing of resources inspace has the potential to greatly reduce thedependency on transporting mission consumables andinfrastructure from Earth, thereby reducing missioncosts, risks, and dependency on Earth.ISRU is Enabling: Through the extraction andprocessing of resources into mission commoditiessuch as rocket propellants, life support consumables,and fuel cell reactants, ISRU enhances and evolvesthe cis-lunar, lander, and surface transportationsystems required for human exploration; expandingand enhancing HOW humans can explore and returnfrom the Moon. Through the extraction andprocessing of resources into metals, silicon, and othermanufacturing and construction feedstock, ISRUenhances and allows for the expansion of criticalinfrastructure using in situ manufacturing andconstruction capabilities that influence WHAT humanscan do on the Moon and in cis-lunar space. Becauseof this, ISRU supports and enables commercialinvolvement beyond NASA and governmentalagencies by both lowering the cost of sustainedtransportation to/from/on the Moon as well assupporting the market required for needing thesetransportation systems. Strategic Framework:To achieve this vision,NASA’s Space Technology Mission Directorate(STMD) ensures the coordinated development ofISRU and other critical space and surfaceinfrastructure elements such as propulsion, power,manufacturing, construction, and robotics through theStrategic Technology Architecture Roundtable(STAR) process. Through STAR, an integratedframework and process has been created allowing forcapabilities and technologies to be linked andassessed, gaps to be identified, specifications andmetrics to be established, and provide a means toprioritize and implement technology development andmissions. A critical part of the STAR effort has beenthe establishment of the Strategic Framework thatorganizes all work under four major Thrusts (Go,Land, Live, and Explore) and identifies the drivingOutcomes for each of these Thrusts. From the Thrustsand Outcomes, all work can be categorized and linkedbetween Capability Areas, and Technology Gaps canbe identified and addressed (Figure 1.)Figure 1. Strategic Framework and STAR FrameworkISRU Envisioned Future: To drive thedevelopment of technologies and capabilities, theSTAR process starts with establishing a ‘grand vision’of where each Outcome and Capability is aiming tobe considered complete. For ISRU, the EnvisionedFuture is “Scalable ISRU production/utilizationcapabilities including sustainable commodities on thelunar and Mars Surface”. This involves starting with10’s of metric tons of products, but evolves into 100’sto 1000’s of metric tons of water, oxygen, propellants,construction and manufacturing feedstock, andcommodities for habitat and food production andoperations. For ISRU, the ‘Prospect to Product’philosophy starts with Destination Reconnaissance &Resource Assessment, followed by ResourceAcquisition, Isolation, and Preparation, leading intoResource Processing (which is further subdivided intomission consumables and feedstocks for constructionand manufacturing). The ISRU Envisioned Futurealso considers what resources are available andattempts to address what and when these resourceswill be evaluated and harnessed, as well asconsidering which products/commodities can beobtained for early use and which ones require moretime and/or users of refined products.It Takes an Architecture: ISRU does not existon its own. By definition, it requires customers/users SHORT TITLE HERE: A. B. Author and C. D. Authorto use the products/commodities produced by ISRUsystems. Also, for an ISRU capability to exist, itmust obtain products and services from other systemsand infrastructure. An important aspect of the STARprocess and the ISRU Envisioned Futures Prioritiesstrategy is to identify and link all of these systems andcapabilities to achieve the desired end state (Figure2).Figure 2. ISRU as Part of a Larger ArchitectureISRU Capability Drivers: The guidingprinciples for NASA’s Space TechnologyDevelopment for Artemis are to develop criticaltechnologies and capabilities that enable (i) asustainable Lunar surface presence, (ii) the future goalof sending humans to Mars, and (iii) promotingcritical technologies to enable future science andcommercial missions. It is a major goal of theArtemis campaign to establish some sort of base campat the lunar South Pole by approximately the end ofthe decade. The ISRU Envisioned Futures Prioritiesstrategy is aligned with the Artemis campaign todevelop and demonstrate ISRU capabilities in thistimeframe that could lead to sustained surfaceoperations, infrastructure growth, and commercialoperations in the next decade (Figure 3).Figure 3. ISRU Dual Path to Full Implementation and CommercializationState of the Art and Gaps: To achieve theenvisioned future, an extensive effort was performedto understand the State of the Art (SOA) for ISRUgoing back decades, and to assess the SOA against thenear and long-term goals and objectives of the ISRUStrategic Outcome objectives. While the releasedISRU Envisioned Futures Priorities only includes atop-level definition of both the SOA and Gaps, furtherinformation on these for ISRU can be found in theISRU Gap Assessment Study performed for theInternational Space Exploration Coordination Group(ISECG) [2]. To provide further guidance to industryand academia, a top level assessment was performedand provide that divides critical areas of ISRUcapabilities and technologies into 3 categories:Significant Funding, Partially Covered/MoreRequired, and Limited/No Funded Activities.Envisioned Future Priorities- Next Steps forISRU: While a significant amount of work over abroad range of technology areas has been performedover the last several years for lunar ISRU, to reach theenvisioned future for ISRU, a lot more work isrequired at the technology level leading to bothsystems and technology demonstrations in the nearfuture. To guide investments within NASA, industry,and academia, 5 specific areas of high priority wereidentified. These are:1.Complete development of the Water and Oxygen Mining Paths and close technology gaps, with emphasis on oxygen extraction from Highland regolith and parallel paths for polar water mining.2.Expand development of metal extraction and feedstock for manufacturing and construction, with emphasis on aluminum and initial/easy to obtain/make construction feedstocks leading to more refined metals and other regolith resources. Also, evaluate biologically inspired/derived technologies in bio-mining, bio-plastic, and other feedstock commodities.3.Ensure the resource assessment needed for future ISRU commercial operations is coordinated with both near/long-term science objectives as well as Artemis mission locations of interest.4.Initiate NASA and industry-led system-level analyses, integration, and testing activities for ISRU capabilities. While significant work has been performed at the technology and subsystemlevel, it is now important to understand how these technology investments can be leveraged and utilized in actual systems and applications5.Initiate lunar ISRU technology flight demonstrations leading to initial ‘Pilot Plant’ end-to-end production capability demonstrations, led by industry

ISRU↗
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↗
DOE OSTI2021

Structure and Stability of Pristine and Carboxylate-Covered Anatase TiO 2 (001) in Aqueous Environment

The interactions of carboxylic acids and water with TiO 2 surfaces are important in applications ranging from solar cells to biomedical devices. Here we focus on the aqueous interface with the minority (001) surface of anatase TiO 2 (A-001) and the behavior of adsorbed formic and acetic acid monolayers at this interface. We investigated the structure and stability of the pristine reconstructed and formic/acetic acid covered A-001 surfaces in contact with water using density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The (1 × 4) reconstruction of the pristine surface is found to be stable in aqueous environment, within the time scale of our simulation. Here, carboxylic acids adsorb in deprotonated bidentate (BD) form on A-001, with the dissociated proton transferred to a surface oxygen to form a bridging hydroxyl. Of the two possible configurations, BD bridging and BD straddling, of the adsorbed species, the latter is found to rapidly transform to a monodentate structure during our simulations. Further investigation of mixed acetate–formate monolayers on A-001 in water indicates that also BD bridging species can become unstable at the boundaries between formate and acetate-covered regions, transforming to a monodentate form that does not prevent water adsorption on the TiO 2 surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

XPS studies of water and oxygen on iron-sputtered natural ilmenite

The adsorption of D2O and O2 on polycrystalline FeTiO3 (natural ilmenite) has been studied by X-ray photoelectron spectroscopy. Oxygen was found to absorb reactively with Fe(0) on Ar(+)-sputtered surfaces at and above 150 K while D2O was found to adsorb molecularly or in ice layers below 170 K on both Ar(+) and O2(+) ion-bombarded ilmenite. The D2O desorbs at 170 K with either the formation of an OD complex or a strongly bound molecular layer of water.

Schulze, P. D.↗
NASA NTRS2012

The Validity Chlorophyll-a Estimation by Sun Induced Fluorescence in Estuarine Waters: An Analysis of Long-term (2003-2011) Water Quality Data from Tampa Bay, Florida (USA)

Satellite observation of phytoplankton concentration or chlorophyll-a is an important characteristic, critically integral to monitoring coastal water quality. However, the optical properties of estuarine and coastal waters are highly variable and complex and pose a great challenge for accurate analysis. Constituents such as suspended solids and dissolved organic matter and the overlapping and uncorrelated absorptions in the blue region of the spectrum renders the blue-green ratio algorithms for estimating chlorophyll-a inaccurate. Measurement of sun-induced chlorophyll fluorescence, on the other hand, which utilizes the near infrared portion of the electromagnetic spectrum, may provide a better estimate of phytoplankton concentrations. While modelling and laboratory studies have illustrated both the utility and limitations of satellite baseline algorithms based on the sun induced chlorophyll fluorescence signal, few have examined the empirical validity of these algorithms using a comprehensive long term in situ data set. In an unprecedented analysis of a long term (2003-2011) in situ monitoring data from Tampa Bay, Florida (USA), we assess the validity of the FLH product from the Moderate Resolution Imaging Spectrometer (MODIS) against chlorophyll ]a and a suite of water quality parameters taken in a variety of conditions throughout a large optically complex estuarine system. A systematic analysis of sampling sites throughout the bay is undertaken to understand how the relationship between FLH and in situ chlorophyll-a responds to varying conditions within the estuary including water depth, distance from shore and structures and eight water quality parameters. From the 39 station for which data was derived, 22 stations showed significant correlations when the FLH product was matched with in situ chlorophyll-alpha data. The correlations (r2) for individual stations within Tampa Bay ranged between 0.67 (n=28, pless than 0.01) and-0.457 (n=12, p=.016), indicating that for some areas within the Bay, FLH can be a good predictor of chlorophyll-alpha concentration and hence a useful tool for the analysis of water quality. Overall, the results show a 106% increase in the validity of chlorophyll -a concentration estimates using FLH over the standard the blue-green OC3M algorithm. This analysis also illustrates that the correlations between FLH and in situ chlorophyll -a measurements increases with increasing water depth and distance of the monitoring sites from both the shore and structures. However, due to confounding factors related to the complexity of the estuarine system, a linear improvement in the FLH to chlorophyll ]a relationship was not clearly noted with increasing depth and distance from shore alone. Correlations of FLH with turbidity, nutrients (total nitrogen and total phosphorous) biological oxygen demand, salinity, sea surface temperature correlated positively with FLH concentrations, while dissolved oxygen and pH showed negative correlations. Principle component analyses are employed to further describe the relationships between the multivariate water quality parameters and the FLH product. The majority of sites with higher and very significant correlations (pless than 0.01) also showed high correlation values for nutrients, turbidity and biological oxygen demand. These sites were on average in greater than seven meters of water and over five kilometers from shore. A thorough understanding of the relationship between the MODIS FLH product and in situ water quality parameters will enhance our understanding of the accuracy MODIS fs global FLH algorithm and assist in optimizing its calibration for use in monitoring the quality of estuarine and coastal waters worldwide.

Moreno-Madrinan, Max Jacobo↗
DOE OSTI2021

A rechargeable zinc-air battery based on zinc peroxide chemistry

When two is better than four Batteries based on the reaction of zinc and oxygen have been used for more than a century, but these have been primary (that is, nonrechargeable) cells. These batteries use an alkaline electrolyte and require a four-electron reduction of oxygen to water, which is a slow process. Sun et al. show that with the right choice of nonalkaline electrolyte, the battery can operate using a two-electron zinc-oxygen/zinc peroxide chemistry that is far more reversible. By making the electrolyte hydrophobic, water is excluded from the near surface of the cathode, thus preventing the four-electron reduction. These batteries also show higher energy density and better cycling stability. Science , this issue p. 46

Science & Technology - Other Topics↗
NASA NTRS1990

Reactions of SiC with H2/H2O/Ar mixtures at 1300 C

Thermochemical modeling anticipates the existence of three reaction regions for the case of a sintered alpha-SiC with 5 percent H2/H2O/Ar at 1300 C, depending on the initial water vapor or, equivalently, oxygen, content of the gas stream. While a high oxygen content leads to SiC-protecting SiO2 surface film formation and limits consumption of the SiC through passive oxidation, intermediate oxygen contents lead to SiO and CO formation and rapid SiC consumption. In this intermediate region, reaction rates appear to be controlled by H2O gas-phase transport to the sample; reacted microstructures exhibit extensive grain-boundary attack in this region. Very low oxygen content is predicted to selectively remove carbon, with free silicon formation.

Jacobson, Nathan S.↗
NASA NTRS1992

SPE water electrolyzers in support of the lunar outpost

During the 1970s, the SPE water electrolyzer, which uses ion exchange membranes as its sole electrolyte, was developed for nuclear submarine metabolic oxygen production. These developments included SPE water electrolyzer operation at up to 3,000 psia and at current densities in excess of 1,000 amps per square foot. The SPE water electrolyzer system is now fully qualified for both the U.S. and U.K. Navies with tens of thousands of system hours accumulated at sea. During the 1980s, the basic SPE water electrolyzer cell structure developed for the Navies was incorporated into several demonstrations for NASA's Space Station Program. Among these were: the SPE regenerative fuel cell for electrical energy storage; the SPE water electrolyzer for metabolic oxygen production; and the high pressure SPE water electrolyzer for reboost propulsion reactant production. In the 1990s, one emphasis will be the development of SPE water electrolyzers for the Lunar Outposts Currently defined potential Lunar Outpost applications for the SPE water electrolyzer include: SPE water electrolyzers for metabolic oxygen and potable water production from reclaimed water; and SPE water electrolyzers operating at high pressure as part of stationary and mobile surface energy storage systems.

Mcelroy, J. F.↗
NASA NTRS2016

Coordinated In Situ Nanosims Analyses of H-C-O Isotopes in ALH 84001 Carbonates

The surface geology and geomorphology of Mars indicate that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. This study reports the hydrogen, carbon, and oxygen isotope compositions of the ancient atmosphere/hydrosphere of Mars based on in situ ion microprobe analyses of approximately 4 Ga-old carbonates in Allan Hills (ALH) 84001. The ALH 84001 carbonates are the most promising targets because they are thought to have formed from fluid that was closely associated with the Noachian atmosphere. While there are a number of carbon and oxygen isotope studies of the ALH 84001 carbonates, in situ hydrogen isotope analyses of these carbonates are limited and were reported more than a decade ago. Well-documented coordinated in situ analyses of carbon, oxygen and hydrogen isotopes provide an internally consistent dataset that can be used to constrain the nature of the Noachian atmosphere/hydrosphere and may eventually shed light on the hypothesis of ancient watery Mars.

Usui, T.↗
NASA NTRSDate not supplied

Anti-Fog Coatings For Spacesuit Helmets

A permanent and robust anti-fog coating was developed that is applied to the interior of polycarbonate spacesuit helmets. The coating is a mechanically resilient and permanent superhydrophilic (SHPL) layer produced by a two-step process consisting of a plasma processing pre-etch followed by the deposition of an optically transparent Diamond Like Carbon (DLC) coating to achieve an anti-fog, SHPL-DLC layer with Water Contact Angle (WCA) < 10°. The all-dry vacuum process consists of an oxygen plasma etching to engineer the surface of the polycarbonate, creating a well-controlled nanotextured morphology, which is key to the superhydrophilic properties, followed by vacuum deposited Plasma Enhanced Chemical Vapor Deposition (PECVD) DLC coating with high surface energy. The process is carried out at low temperatures compatible with polycarbonate materials and the two steps are performed back-to-back without breaking vacuum between steps. The process is readily scalable and compatible with large scale production volumes. The SHPL-DLC coating was tested for > 200 hours exposure using a breath simulator with no detrimental effect on the coating performance. The coating was also tested for exposure to cleaning fluids, IPA chemical exposure, adhesion testing per ASTM D3359, and abrasion resistance per MIL-E-12397 with no detrimental effects.

Spacesuit↗
DOE OSTI2024

Influence of Annealing Temperature on the OER Activity of NiO(111) Nanosheets Prepared via Microwave and Solvothermal Synthesis Approaches

Earth-abundant transition metal oxides are promising alternatives to precious metal oxides as electrocatalysts for the oxygen evolution reaction (OER) and are intensively investigated for alkaline water electrolysis. OER electrocatalysis, like most other catalytic reactions, is surface-initiated, and the catalyst performance is fundamentally determined by the surface properties. Most transition metal oxide catalysts show OER activities that depend on the predominantly exposed crystal facets/surface structure. Therefore, the design of synthetic strategies to obtain the most active crystal facets is of significant research interest. In this work, rock salt NiO OER catalysts with (111) predominantly exposed facets were synthesized by a solvothermal (ST) method either heated under supercritical or microwave-assisted (MW) conditions. Particular emphasis was placed on the influence of the post annealing temperature on the structural configuration and OER activity to compare their catalytic performances. The as-prepared electrocatalysts are pure α-Ni hydroxides which were converted to rock salt NiO (111) nanosheets with hexagonal pores after heat treatment at different temperatures. The OER activity of the electrodes has been evaluated in 0.1 M KOH using geometric and intrinsic current densities via normalization by the disk area and BET area, respectively. The lowest overpotential at a geometric current density of 10 mA/cm 2 is found for samples pretreated by heating between 400 and 500 °C with a catalyst loading of 115 μg/cm 2 . Despite the very similar nature of the catalysts obtained from the two methods, the ST electrodes show a higher geometric and intrinsic current density for 500 °C pretreatment. The MW electrodes, however, achieve an optimal geometric current density for 400 °C pretreatment, while their intrinsic current density requires pretreatment over 600 °C. Interestingly, pretreated electrodes show consistently higher OER activity as compared to the poorly crystalline/less ordered hydroxide as-prepared electrocatalysts. Thus, our study highlights the importance of the synthesis method and pretreatment at an optimal temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Morphological Modulation of TiO 2 Nanotube via Optimal Anodization Condition for Solar Water Oxidation

With the depletion of fossil fuels and the rising global demand for energy, photoelectrochemical (PEC) water splitting presents a promising solution to avert an energy crisis. Titanium dioxide (TiO 2 ), an n -type semiconductor, has gained popularity as a photoanode due to its remarkable PEC properties. Nevertheless, inherent challenges such as a wide band gap (~3.2 eV), charge recombination, and slow oxygen evolution reaction (OER) rates at the surface limit its practical application by constraining light absorption. To overcome these limitations, we have developed TiO 2 nanotubes (NTs) using a facile anodization method. This study examines the impact of anodization growth parameters on solar water oxidation performance. Specifically, TiO 2 NTs with modified anodization time (referred to as TiO 2 -6) showed a 3.5-fold increase in photocurrent density compared to the as-grown TiO 2 NTs. Furthermore, electrochemical analyses, such as electrochemical impedance spectroscopy (EIS), indicated a significant decrease in charge transfer resistance following the adjustment of on-off anodization time. Additionally, the TiO 2 -6 photoanode demonstrated a higher electrochemically active surface area (ECSA) than other samples. Therefore, optimal nanostructuring parameters are crucial for enhancing the PEC properties of TiO 2 NTs. Overall, our findings offer valuable insights for fabricating high-quality TiO 2 NTs photoanodes, contributing to developing efficient PEC systems for sustainable energy production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

An ISRU Propellant Production System to Fully Fuel a Mars Ascent Vehicle

ISRU of Mars resources was base lined in 2009 Design Reference Architecture (DRA) 5.0, but only for Oxygen production using atmospheric CO2The Methane (LCH4) needed for ascent propulsion of the Mars Ascent Vehicle (MAV) would need to be brought from Earth. HOWEVER: Extracting water from the Martian Regolith enables the production of both Oxygen and Methane from Mars resources Water resources could also be used for other applications including: Life support, radiation shielding, plant growth, etc. Water extraction was not base lined in DRA5.0 due to perceived difficulties and complexity in processing regolith. The NASA Evolvable Mars Campaign (EMC) requested studies to look at the quantitative benefits and trades of using Mars water ISRU Phase 1: Examined architecture scenarios for regolith water retrieval. Completed October 2015Phase 2: Deep dive of one architecture concept to look at end-to-end system size, mass, power of a LCH4LO2 ISRU production system.Evolvable Mars CampaignPre-deployed Mars ascent vehicle (MAV)4 crew membersPropellants: Oxygen MethaneGenerate a system model to roll up mass power of a full ISRU system and enable parametric trade studies. Leverage models from previous studies and technology development programs Anchor with mass power performance from existing hardware. Whenever possible used reference-able (published) numbers for traceability.Modular approach to allow subsystem trades and parametric studies. Propellant mass needs taken from most recently published MAV study:Polsgrove, T. et al. (2015), AIAA2015-4416MAV engines operate at mixture ratios (oxygen: methane) between 3:1 and 3.5:1, whereas the Sabatier reactor produces at a 4:1 ratio. Therefore:Methane production is the driving requirement-Excess Oxygen will be produced.

Mars surface↗
DOE OSTI2020

Work function measurements of clean and modified carbon nanospikes

Carbon surfaces incorporating densely packed spikes with nanometer sharpness have shown exceptional electrocatalytic properties attributed to the enhanced electric field from the topography of the spikes. In this article, the composition of nanospike surfaces is identified by x-ray photoelectron spectroscopy (XPS) and their absolute work function determined using ultraviolet photoemission spectroscopy (UPS). Low temperature annealing of as-grown samples above 275 °C is required to produce a clean surface which has a 4.13 eV work function, a half volt lower than that of flat graphite. Treatments that contaminate the spiked surface, including exposure to air, oxidation at elevated temperature, or immersion in water or hydrocarbons, all increase the work function. Processing that blunts the spikes, including exposure to an oxygen plasma, argon sputtering, or high temperature annealing (800 °C) result in a work function close to that of flat graphite. An unusual double onset in the UPS secondary electron intensity is observed on as-grown nanospike samples and is reproduced by absorbing hydrocarbons on the surface. In conclusion, this double onset appears to be unique to carbon substrates and may originate in inelastic scattering of photoelectrons.

36 MATERIALS SCIENCE↗