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At least 667 records · Page 37

Understanding methanol dissociative adsorption and oxidation on amorphous oxide films

Interactions between a transition metal (oxide) catalyst and a support can tailor the number and nature of active sites, for instance in the methanol oxidation reaction.In this report we use ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify and compare the surface adsorbates that form on amorphous metal oxide films that maximize such interactions. Considering Al (1−x) M x O y (M = Fe or Mn) films at a range of methanol : oxygen gas ratios and temperatures, we find that the redox-active transition metal site (characterized by methoxy formation) dominates dissociative methanol adsorption, while basic oxygen sites (characterized by carbonate formation) play a lesser role. Product detection, however, indicates complete oxidation to carbon dioxide and water with partial oxidation products (dimethyl ether) comprising a minor species. Comparing the intensity of methoxy and hydroxyl features at a fixed XPS chemical shift suggests methanol deprotonation during adsorption in oxygen rich conditions for high transition metal content. However, increasing methanol partial pressure and lower metal site density may promote oxygen vacancy formation and the dehydroxylation pathway, supported by a nominal reduction in the oxidation state of iron sites. These findings illustrate that AP-XPS and mass spectrometry together are powerful tools in understanding metal–support interactions, quantifying and probing the nature of catalytic active sites, and considering the link between electronic structure of materials and their catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Decadal Evolution of the Surface Energy Budget During the Fast Warming and Global Warming Hiatus Periods in the ERA-Interim

The global-mean surface temperature has experienced a rapid warming from the 1980s to early-2000s but a muted warming since, referred to as the global warming hiatus in the literature. Decadal changes in deep ocean heat uptake are thought to primarily account for the rapid warming and subsequent slowdown. Here, we examine the role of ocean heat uptake in establishing the fast warming and warming hiatus periods in the ERA-Interim through a decomposition of the global-mean surface energy budget. We find the increase of carbon dioxide alone yields a nearly steady increase of the downward longwave radiation at the surface from the 1980s to the present, but neither accounts for the fast warming nor warming hiatus periods. During the global warming hiatus period, the transfer of latent heat energy from the ocean to atmosphere increases and the total downward radiative energy flux to the surface decreases due to a reduction of solar absorption caused primarily by an increase of clouds. The reduction of radiative energy into the ocean and the surface latent heat flux increase cause the ocean heat uptake to decrease and thus contribute to the slowdown of the global-mean surface warming. Our analysis also finds that in addition to a reduction of deep ocean heat uptake, the fast warming period is also driven by enhanced solar absorption due predominantly to a decrease of clouds and by enhanced longwave absorption mainly attributed to the air temperature feedback.

Hu, Xiaoming↗

Gas-Liquid Supersonic Cleaning and Cleaning Verification Spray System

NASA Kennedy Space Center (KSC) recently entered into a nonexclusive license agreement with Applied Cryogenic Solutions (ACS), Inc. (Galveston, TX) to commercialize its Gas-Liquid Supersonic Cleaning and Cleaning Verification Spray System technology. This technology, developed by KSC, is a critical component of processes being developed and commercialized by ACS to replace current mechanical and chemical cleaning and descaling methods used by numerous industries. Pilot trials on heat exchanger tubing components have shown that the ACS technology provides for: Superior cleaning in a much shorter period of time. Lower energy and labor requirements for cleaning and de-scaling uper.ninih. Significant reductions in waste volumes by not using water, acidic or basic solutions, organic solvents, or nonvolatile solid abrasives as components in the cleaning process. Improved energy efficiency in post-cleaning heat exchanger operations. The ACS process consists of a spray head containing supersonic converging/diverging nozzles, a source of liquid gas; a novel, proprietary pumping system that permits pumping liquid nitrogen, liquid air, or supercritical carbon dioxide to pressures in the range of 20,000 to 60,000 psi; and various hoses, fittings, valves, and gauges. The size and number of nozzles can be varied so the system can be built in configurations ranging from small hand-held spray heads to large multinozzle cleaners. The system also can be used to verify if a part has been adequately cleaned.

Parrish, Lewis M.↗

ISRU Propellant Selection for Space Exploration Vehicles

Chemical propulsion remains the only viable solution as technically matured technology for the near term human space transportation to Lunar and Mars. Current mode of space travel requires us to "take everything we will need", including propellant for the return trip. Forcing the mission designers to carry propellant for the return trip limits payload mass available for mission operations and results in a large and costly (and often unaffordable) design. Producing propellant via In-Situ Resource Utilization (ISRU) will enable missions with chemical propulsion by the "refueling" of return-trip propellant. It will reduce vehicle propellant mass carrying requirement by over 50%. This mass reduction can translates into increased payload to enhance greater mission capability, reduces vehicle size, weight and cost. It will also reduce size of launch vehicle fairing size as well as number of launches for a given space mission and enables exploration missions with existing chemical propulsion. Mars remains the ultimate destination for Human Space Exploration within the Solar System. The Mars atmospheric consist of 95% carbon dioxide (CO2) and the presence of Ice (water) was detected on Mars surfaces. This presents a basic chemical building block for the ISRU propellant manufacturing. However, the rationale for the right propellant to produce via ISRU appears to be limited to the perception of "what we can produce" as oppose to "what is the right propellant". Methane (CH4) is often quoted as a logical choice for Mars ISRU propellant, however; it is believed that there are better alternatives available that can result in a better space transportation architecture. A system analysis is needed to determine on what is the right propellant choice for the exploration vehicle. This paper examines the propellant selection for production via ISRU method on Mars surfaces. It will examine propellant trades for the exploration vehicle with resulting impact on vehicle performance, size, and on launch vehicles. It will investigate propellant manufacturing techniques that will be applicable on Mars surfaces and address related issues on storage, transfer, and safety. Finally, it will also address the operability issues associated with the impact of propellant selection on ground processing and launch vehicle integration.

Chen, Timothy T.↗

Risk Reduction of Orion Multi-Purpose Crew Vehicle (MPCV) Program Government-Furnished Equipment for Environmental Control and Life Support (ECLS)

The NASA Engineering and Safety Center (NESC) was requested to conduct technical risk-reduction activities for safety-critical government-furnished environmental control and life support (ECLS) equipment for the Multi-Purpose Crew Vehicle Program. These items include the post-landing anomaly gas monitor, the in-flight anomaly gas monitor, the emergency breathing mask, the 144-hour in-suit survival capability, the portable fire extinguisher, the smoke eater, and the post-landing carbon dioxide control system. This document contains the outcome of the NESC assessment.

Environmental Control and Life Support↗

Abstract for CRADA between Mati Car bon PBC and NETL

The National Energy Technology Laboratory (NETL) will assist Mati Carbon PBC (participant) in the design and execution of their community benefits plan (CBP) for scaling Enhanced Rock Weathering (ERW) carbon dioxide removal (CDR) in Arkansas. ERW involves spreading finely crushed rocks in agricultural fields to speed up the dissolution and release of certain minerals that amend soil acidity, replenish soil nutrients, and simultaneously converting CO 2 from the atmosphere to Dissolved Inorganic Carbon (DIC). ERW not only removes CO 2 from the atmosphere but also has the potential to generate co-benefits for famers through cost reductions and increased crop yields. The collaboration between NETL and Mati Carbon, PBC (participant) will entail a detailed review of the economic, environmental and community impact of ERW in agricultural settings. This review will guide all project related decisions. It will provide a better understanding of the scale of these potential co-benefits and quantify community needs that ERW can address.

54 ENVIRONMENTAL SCIENCES↗

Mars ISRU for Production of Mission Critical Consumables - Options, Recent Studies, and Current State of the Art

In 1978, a ground breaking paper titled, "Feasibility of Rocket Propellant Production on Mars" by Ash, Dowler, and Varsi discussed how ascent propellants could be manufactured on the Mars surface from carbon dioxide collected from the atmosphere to reduce launch mass. Since then, the concept of making mission critical consumables such as propellants, fuel cell reactants, and life support consumables from local resources, commonly known as In-Situ Resource Utilization (ISRU), for robotic and human missions to Mars has been studied many times. In the late 1990's, NASA initiated a series of Mars Human Design Reference Missions (DRMs), the first of which was released in 1997. These studies primarily focused on evaluating the impact of making propellants on Mars for crew ascent to Mars orbit, but creating large caches of life support consumables (water & oxygen) as a backup for regenerative life support systems for long-duration surface stays (>500 days) was also considered in Mars DRM 3.0. Until science data from the Mars Odyssey orbiter and subsequent robotic missions revealed that water may be widely accessable across the surface of Mars, prior Mars ISRU studies were limited to processing Mars atmospheric resources (carbon dioxide, nitrogen, argon, oxygen, and water vapor). In December 2007, NASA completed the Mars Human Design Reference Architecture (DRA) 5.0 study which considered water on Mars as a potential resource for the first time in a human mission architecture. While knowledge of both water resources on Mars and the hardware required to excavate and extract the water were very preliminary, the study concluded that a significant reduction in mass and significant enhancements to the mission architecture were possible if Mars water resources were utilized. Two subsequent Mars ISRU studies aimed at reexamining ISRU technologies, processing options, and advancements in the state-of-the-art since 2007 and to better understand the volume and packaging associated with Mars ISRU systems further substantiated the preliminary results from the Mars DRA 5.0 study. This paper will provide an overview of Mars ISRU consumable production options, the analyses, results, and conclusions from the Mars DRA 5.0 (2007), Mars Collaborative (2013), and Mars ISRU Payload for the Supersonic Retro Propulsion (2014) mission studies, and the current state-of-the-art of Mars ISRU technologies and systems. The paper will also briefly discuss the mission architectural implications associated with Mars resource and ISRU processing options.

Sanders, G. B.↗

Designing Heteroatom-Codoped Iron Metal–Organic Framework for Promotional Photoreduction of Carbon Dioxide to Ethylene

Rational engineering active sites and vantage defects of catalysts are promising but grand challenging task to enhance photoreduction CO 2 to high value-added C2 products. In this study, we designed an N,S-codoped Fe-based MIL-88B catalyst with well-defined bipyramidal hexagonal prism morphology via a facile and effective process, which was synthesized by addition of appropriate 1,2-benzisothiazolin-3-one (BIT) and acetic acid to the reaction solution. Under simulated solar irradiation, the designed catalyst exhibits high C 2 H 4 evolution yield of 17.7 μmol g -1 ∙h, which has been rarely achieved in photocatalytic CO 2 reduction process. The synergistic effect of Fe-N coordinated sites and reasonable defects in the N,S-codoped photocatalyst can accelerate the migration of photogenerated carriers, resulting in high electron density, and this in turn helps to facilitate the formation and dimerization of C-C coupling intermediates for C 2 H 4 effectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New Evidence for the Importance of Non-Stomatal Pathways in Ozone Deposition During Extreme Heat and Dry Anomalies

Dry deposition could partially explain the observed response in ambient ozone to extreme hot and dry episodes. We examine the response of ozone deposition to heat and dry anomalies using three long-term co-located ecosystem-scale carbon dioxide, water vapor and ozone flux measurement records. We find that, as expected, canopy stomatal conductance generally decreases during days with dry air or soil. However, during hot days, concurrent increases in non-stomatal conductance are inferred at all three sites, which may be related to several temperature-sensitive processes not represented in the current generation of big-leaf models. This may offset the reduction in stomatal conductance, leading to smaller net reduction, or even net increase, in total deposition velocity. We find the response of deposition velocity to soil dryness may be related to its impact on photosynthetic activity, though considerable variability exists. Our findings emphasize the need for better understanding and representation of non-stomatal ozone deposition.

54 ENVIRONMENTAL SCIENCES↗

Carbon Removal Accounting for a Sustainable Future: Distributing CO 2 Flows in Multiservice Systems

Carbon dioxide removal (CDR) systems are an integral part of sustainable pathways limiting global warming to less than 2.0 °C. When the sole purpose of CDR is capturing and storing atmospheric CO 2 , carbon registries offer detailed procedures to calculate the carbon removal credits. However, the registries do not address how to distribute CO 2 flows when CDR provides additional services. Standardized, transparent rules for distributing CO 2 flows among CDR services are required for the formation of efficient private and public carbon markets. The lack of such rules could result in double counting if those reductions are allocated to more than one service, decreasing the trustworthiness of carbon removal credits or deterring the delivery of an additional low-carbon service, thus limiting the economic viability and deployment of CDR. We examine allocation rules in carbon registries and carbon accounting guidelines, including their life cycle assessment (LCA) principles. We evaluate physical (mass-based) and non-physical (economic) allocation methods using a generic CDR system and find both to be unworkable. We then develop a mass balance (MB) approach which can reliably allocate captured and stored carbon (CSC) between carbon removal credits and other services based on the value CO 2 removal in those markets. This practical approach to allocation can be used in a transparent way to provide flexibility that would allow CDR services to capture the value of the multiple services they provide and, through this, promote the deployment of these sustainable alternatives.

54 ENVIRONMENTAL SCIENCES↗

Enhancing carbon nanotube production from carbon dioxide and ethane using bimetallic catalysts

Converting CO 2 into carbon nanotubes (CNTs) offers a promising way for CO 2 utilization and sequestration, potentially mitigating environmental impacts from anthropogenic emissions. This study reports that bimetallic CoFe catalysts can increase CNT production from the reaction of CO 2 and C 2 H 6 by an order of magnitude compared to their monometallic counterparts. The active sites and CNT morphologies are composition-dependent: Co-rich catalysts (Co/Fe ratio ≥ 5) form stable face-centered cubic (fcc) CoFe alloys, producing cylindrical CNTs; Fe-containing catalysts (Co/Fe ≤ 2) favor body-centered cubic (bcc) CoFe alloy upon reduction, which transforms into carbides, resulting in bamboo-like CNTs. Experimental evidence and DFT calculations reveal that adjacent Fe and Co atoms modulate CO and C x H y adsorption, regulating CNT production pathways through the CO Boudouard reaction and C 2 H 6 decomposition. In conclusion, these results highlight the dual benefits of bimetallic catalysts in enhancing CNT yield and controlling CNT morphology through adjustment of catalyst compositions.

58 GEOSCIENCES↗

Cyanobacterial mats: Microanalysis of community metabolism

The microbial communities in two sites were studied using several approaches: (1) light microscopy; (2) the measurement of microprofiles of oxygen and sulfide at the surface of the microbial mat; (3) the study of diurnal variation of oxygen and sulfides; (4) in situ measurement of photosynthesis and sulfate reduction and study of the coupling of these two processes; (5) measurement of glutathione in the upper layers of the microbial mat as a possible oxygen quencher; (6) measurement of reduced iron as a possible intermediate electron donor along the established redoxcline in the mats; (7) measurement of dissolved phosphate as an indicator of processes of break down of organic matter in these systems; and (8) measurement of carbon dioxide in the interstitial water and its delta C-13 in an attempt to understand the flow of CO2 through the systems. Microbial processes of primary production and initial degradation at the most active zone of the microbial mat were analyzed.

Cohen, Y.↗

Techno-Economic Evaluation of Strategies to Approach Net-Zero Carbon Sustainable Aviation Fuel via Woody Biomass Gasification and Fischer-Tropsch Synthesis

Reducing the carbon dioxide (CO2) emissions from the transportation industry is a key target for achieving global net-zero carbon goals. Wide-spread electrification, efficient engine design, and alternative fuel implementations have been introduced for light-duty vehicles and are projected to significantly reduce light-duty emissions in the near future. Conversely, the aviation sector contributes considerably towards transportation-based carbon emissions, but current projections do not show substantial reductions in carbon emissions over time. Challenges for the aviation sector include low compatibility with electrification, relative inflexibility to variations in fuel properties, and requirement of high energy density fuels. Thus, identifying pathways to decarbonize the aviation sector via liquid low- or net-zero carbon biofuels that are compatible with current aviation infrastructure is crucial. This work investigates the economic feasibility of approaching net-zero carbon sustainable aviation fuel (SAF) from woody biomass via gasification and Fischer-Tropsch synthesis. In doing so, this assessment identifies the economic opportunities and trade-offs of several carbon mitigation strategies coupled with renewable resource interventions required to approach net-zero carbon fuels via biomass. Renewable natural gas and green hydrogen utilization strategies are assessed to examine the impact of fuel yield improvements versus renewable resource cost. Additionally, both carbon capture and sequestration (CCS) and carbon capture and utilization (CCU) are considered in this analysis to help mitigate carbon loss to the atmosphere. Each scenario was assessed on cost, carbon efficiency, energy efficiency, and overall technology-readiness level (TRL). The results of this analysis show that renewable natural gas, green hydrogen, and CCS can be viewed as a low-cost, near-term carbon abatement strategies. However, in the long-term, deployment of more expensive and less technologically mature CCU technologies can make use of point sources of CO2 to boost overall fuel production.

aviation fuel↗

Ba₁₋ₓSrₓFeO₃₋ᵧ as an Improved Oxygen Carrier for Chemical Looping Air Separation: A Computational and Experimental Study

Chemical looping air separation (CLAS) is a promising method to generate pure carbon-dioxide from fuel combustion with a pure oxygen stream, which is produced through the capture, and targeted release, of oxygen from the atmosphere using a solid oxide carrier. The performance of this process depends on the redox characteristics of the oxide carrier. Using experimental oxygen-temperature-programmed desorption (TPD) and thermogravimetric analysis (TGA), the study shows that Ba₀․₇₅Sr₀․₂₅FeO₃ has improved oxygen storage capacity (OSC), oxidation, and reduction kinetics over pristine SrFeO₃ at temperatures ranging from 300-500 °C. The redox energetics computed by using first-principles density functional theory (DFT) calculations also depict the measured trend establishing it as an important descriptor of the measured performance. The Ba₁₋ₓSrₓFeO₃₋ᵧ depicts a Sr-substitution and oxygen stoichiometry induced structural phase transition from hexagonal at low temperatures to pseudo-cubic phase with higher OSC up to T=400 °C. Also, the mechanism leading to this structural phase transition is identified by performing electronic and vibrational structural calculations. This presentation was given on March 8, 2024 at the APS March Meeting in Minneapolis, MN.

Acharya, Shree Ram↗

Tuning the hydrogenation of CO 2 to CH 4 over mechano-chemically prepared palladium supported on ceria

CO 2 methanation reactivity, reaction mechanism, and surface structure were investigated on a mechanochemically prepared Pd/CeO 2 catalyst (PdAcCeO 2 -M), where an oxidative pretreatment (-o) increased methane yield by a factor of two compared to a reductive pretreatment (-h). Methanation rates were maintained for over 48 h and further increased upon oxidative regeneration treatments. The surface species of both PdAcCeO 2 -M-o and PdAcCeO 2 -M-h were explored via in situ CO 2 and CO hydrogenation DRIFTS, where CO hydrogenation effectively models the dissociative CO 2 mechanism (CO 2 → CO → CH 4 ). PdAcCeO 2 -M-o yielded distinct Pd-CO adsorption and the absence of monodentate carbonate at ~ 1400 cm -1 , while AP-XPS showed that PdAcCeO 2 -M-o yielded a unique Pd δ+ contribution at 335.9 eV. By gaining insights from various in situ spectroscopic techniques, and by breaking the CO 2 hydrogenation mechanism into piecewise steps, a deeper understanding of the direct CO 2 reduction towards methane and CO over mechanochemically prepared Pd/CeO 2 catalysts was obtained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energy savings and life cycle cost analysis of advanced double skin facade system applied to old apartments in South Korea

South Korea is one of the most densely populated countries in the world, and the population density in urban areas is much higher among others. Apartments are the most common form of residential buildings due to their high population density. More than 60% of domestic residential buildings are apartments, with more than 10 million households. The high population density is a problem that has long plagued South Korea because more than 45% of apartments are old apartments that are more than 20 years old. Old apartment buildings have low thermal performance that results in lots of energy consumption. Balconies, which worked as a thermal buffer, are also being removed by residents to expand indoor space. According to the green remodeling project supported by the Korean government, the typical retrofitting method is replacing external windows with the high-efficiency window in old apartments in South Korea. Here, this paper proposes a retrofitting method using an extended double-skin façade (DSF) system that replaces exterior windows and acts as a thermal buffer. The simulation model is developed with the EnergyPlus simulation program to conduct energy performance analyses. The simulation model has been calibrated using actual experimental data collected between October 1, 2019, and January 15, 2020. Results show that the cooling, heating, and lighting energy can be reduced up to 44.1% by fully utilizing electric energy generated by solar PV panels integrated with the DSF system. The payback period is about 15 years based on the energy price provided by the utility company. Although the payback period is long, it has great potential of energy savings and CO 2 emission reductions. The DSF system should be considered as a way of renovation, considering other factors such as increased real estate values and energy cost increases in the future.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Diesel Passenger Vehicle Shares Influenced Covid-19 Changes in Urban Nitrogen Dioxide Pollution

Diesel-powered vehicles emit several times more nitrogen oxides than comparable gasoline-powered vehicles, leading to ambient nitrogen dioxide (NO2) pollution and adverse health impacts. The COVID-19 pandemic and ensuing changes in emissions provide a natural experiment to test whether NO2 reductions have been starker in regions of Europe with larger diesel passenger vehicle shares. Here we use a semi-empirical approach that combines in-situ NO2 observations from urban areas and an atmospheric composition model within a machine learning algorithm to estimate business-as-usual NO2 during the first wave of the COVID-19 pandemic in 2020. These estimates account for the moderating influences of meteorology, chemistry, and traffic. Comparing the observed NO2 concentrations against business-as-usual estimates indicates that diesel passenger vehicle shares played a major role in the magnitude of NO2 reductions. European cities with the five largest shares of diesel passenger vehicles experienced NO2 reductions ∼ 2.5 times larger than cities with the five smallest diesel shares. Extending our methods to a cohort of non-European cities reveals that NO2 reductions in these cities were generally smaller than reductions in European cities, which was expected given their small diesel shares. We identify potential factors such as the deterioration of engine controls associated with older diesel vehicles to explain spread in the relationship between cities’ shares of diesel vehicles and changes in NO2 during the pandemic. Our results provide a glimpse of potential NO2 reductions that could accompany future deliberate efforts to phase out or remove passenger vehicles from cities.

Nitrogen Dioxide↗

The CapiSorb Visible System (CVS) Demonstrations on ISS

Falling liquid film amine sorbent reactors have been successfully employed to scrub CO 2 aboard submarines for decades. However, applying such proven methods aboard orbiting and coast spacecraft is significantly challenged by the nearly weightless environment, where liquid sprays and films do not fall, and vapor bubbles and gases do not rise. The Capillary Sorbent (CapiSorb) Visible System (CVS) is a technology demonstration experiment performed aboard the ISS April 18 – 21, 2023. The system establishes stable steady thin liquid film flows in Contactor (absorber) and Degasser (desorber/stripper) replacing the passive role of gravity with the combined passive roles of surface tension, wetting, and system geometry. A TOX-0 fructose ersatz liquid sorbent is employed enabling ‘transparent’ experiments performed and filmed by the crew safely in the open cabin of the ISS. Completed objectives include demonstrations of stable passive ‘massively’ parallel planar thin film capillary flows across atmospheric pressure Contactor and sealed heated Degasser. The impacts of varying flow rate, flow direction, heat input, viscosity, positive and negative Degasser pressures, condensate collection and return, fluid distribution, interfacial stability, and others are reported. At least 49 diagnostics are recorded for digitization and subsequent thermal-fluids model validation by a single HD video downlink during the nearly 22 hours of operations. An overview of the flight hardware including description of the components, diagnostics, crew procedures, flight operations, and summary of accomplishments is reported in Ref. 1. Further details of the diagnostics, tests performed, and data reduction is reported in Ref. 2. This report collects both1,2 into a single report adding methods of data digitization, reduction, and archive along with analyses and discussions of technology impacts.

microgravity↗