Results for “supports” — Page 14

NASA NTRSDate not supplied

Examining the Trends in Financial Support Given to Science Teams for Data Analysis in Mission Proposals

Introduction: The goal of this summer internship research project was to analyze trends in financial support proposed for the science teams of planetary missions. The analysis focuses on the funding for Co-Investigators (Co-Is) to conduct research and/or data analysis needed to achieve the science objectives of the mission. The operational portion of the missions after launch (i.e., Phase E, including cruise and prime operations at the final destination) were examined since that is when the bulk of research is funded and conducted. The objectives of the project were to determine the average level of support for Co-Investigators, identify variation between mission competitions and over time, and determine the relationship between mission type and the amount of support requested. Methodology: This project was conducted using data from 90 proposals submitted to six mission competitions in the Discovery and New Frontiers programs. The level of support for Co-Is was determined by examining Work Breakdown Structure (WBS) 4 (Science Analysis) for Phase E, which was further subdivided into cruise and prime operations. This data represents a proxy rather than the actual funding Co-Is receive to perform research and data analysis because not every dollar in WBS 4 is spent on this activity. Therefore, the proxy obtained in this research represents an overestimate of the funds allocated to Co-Is for research and data analysis. Findings: Analysis shows that on average a Co-I receives approximately four full years of support spread across the entirety of Phase E for science analysis. The variation among proposed missions is less than expected given the variety of factors that are expected to drive this metric (length of mission, mission type, etc.). Additionally, the level of requested support for Co-Is has been remarkably consistent across every variable considered (by competition, over time, by mission type) over the six competitions and nearly 20 years spanned by this project. This remains true for cruise, primary operations, and all of Phase E. Conclusions: A remarkable amount of science is accomplished by the science teams of planetary missions. However, a surprisingly small amount of funding is requested to support the science analysis driving this productivity, both in terms of absolute magnitude of funding and as a portion of total mission cost. This suggests improvements are needed to refine the estimates of Co-I support and/or that Co-Is rely on other funding sources to conduct their research. Better estimates can be determined by engaging directly with Co-Is and NASA centers to obtain data as well as finding other data sources. Additionally, NASA could consider mandating improved reporting of requested funding levels in mission competitions.

E Murray↗

DOE OSTI2020

Heterolytic Hydrogen Activation: Understanding Support Effects in Water–Gas Shift, Hydrodeoxygenation, and CO Oxidation Catalysis

Identifying the role of oxide supports in transition metal catalysis is critical toward our understanding of heterogeneous catalysis. The water-gas shift (WGS) reaction is a prototypical example where oxide support dictates catalytic activity, yet the cause for this remains uncertain. Herein, we show that a single descriptor—the equilibrium constant for hydroxyl formation—relates the WGS turnover frequency across disparate oxide supports. The dissimilar equilibrium constant, or oxophilicity, between early and late transition metals exemplify the utility of metal-support interfacial sites to circumvent adsorption-energy scaling restrictions, thereby providing bifunctional gains for the WGS reaction class. In relation, the equilibrium constant for hydroxyl formation is equivalent to the equilibrium constant for the formal heterolytic dissociation of hydrogen, and therefore, reflects the ability of the metal-support interface to participate in hydrogen heterolysis. The ubiquitous coexistence, yet divergent chemical behavior of homo- and heterolytically activated hydrogen renders oxide support identity central toward our understanding of hydrogenation catalysis. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and performed at the Environmental Molecular Sciences Laboratory in (EMSL), which is a DOE Office of Science User Facility located at the Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided by a user proposal at the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility. N.N. would like to thank Oliver Y. Gutierrez for critical feedback during the final stage of manuscript preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Mechanistic understanding of support effect on the activity and selectivity of indium oxide catalysts for CO 2 hydrogenation

Herein we present a mechanistic study on the support effect (ZrO 2 and CeO 2 ) of In 2 O 3 catalysts in CO 2 hydrogenation by a combined experimental and computational approach. Kinetic experiments and surface characterization suggested that the activity of In 2 O 3 catalysts cannot be simply correlated with the abundance of surface oxygen vacancies (O v ) formed by either H 2 -reduction or thermal treatment, which has been frequently invoked in previous studies. The support effect should originate from the electronic interactions between In 2 O 3 and the support oxide, rather than geometric factors or the difference in the particle size of In 2 O 3 . Theoretical modelling revealed that surface O v facilitate the formation and stabilization of the formate (HCOO*) intermediate. While a carbonate-like structure is favored for CO 2 adsorption on CeO 2 -supported or unsupported In 2 O 3 catalysts, CO 2 tends to bind strongly in a bent configuration on the O v site at the In 2 O 3 -ZrO 2 interface. The distinct CO 2 adsorption structures on different supported In 2 O 3 catalysts may account for the different reaction energy profiles in the subsequent hydrogenation reactions, especially the rate-limiting step, i.e., hydrogenation of HCOO* to CH 2 O* and methoxy (CH 3 O*). The relatively higher methanol selectivity of In 2 O 3 catalyst supported on ZrO 2 with respect to that on CeO 2 are suggested to stem from the greater energy difference (Δ$E_a$) between the parallel hydrogenation and C-O bond cleavage of HCOO*, which leads to the formation of methanol and CO, respectively. We report this study underlines the important role of metal-oxide-interface in determining the catalytic behavior of oxide-supported In 2 O 3 catalysts in CO 2 conversion.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2021

Not all platinum surfaces are the same: Effect of the support on fundamental properties of platinum adlayer and its implications for the activity toward hydrogen evolution reaction

The adsorption of atomic hydrogen on a platinum monolayer supported on orthorhombic Mo 2 C(100) surface has been investigated, considering different hydrogen surface coverages. Calculations have been performed using density functional theory with the Perdew-Burke-Ernzerhof exchange correlation functional and a D3 Van der Waals corrections. The theoretical insight has been gained into atomic hydrogen interaction with Pt monolayer, supported on both molybdenum and well-studied tungsten carbide, and considering hydrogen surface coverage. Fundamental properties of Pt adlayer depend on the support, affecting hydrogen evolution activity of the resulting systems. At low hydrogen coverage all systems, with the exception of Pt supported on the molybdenum-terminated Mo 2 C, adsorb H comparably to a pristine Pt(111) surface and their high activity for the hydrogen evolution reaction is predicted. Additionally, at higher coverages supported Pt monolayers interact with atomic hydrogen unlike the Pt(111), suggesting that the activity of the supported and unsupported platinum toward hydrogen evolution reaction have different origins. Furthermore, the position of the supported platinum monolayers on the volcano curve is a function of the surface coverage, more so than for extended metal surfaces. Therefore, hydrogen surface coverage is a key variable to understand the catalytic potential, approaching towards an improved model for screening of electrocatalytic systems.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Supported Metal Pair-Site Catalysts

Complexes with neighboring metal centers in isolated pairs and their analogues on surfaces are drawing increasing attention as catalysts. These include molecular homogeneous catalysts incorporating various ligands, enzymes, and solids that include pairs of metal atoms mounted on supports. Catalysts in this broad class are active for numerous reactions and offer unexplored opportunities to address challenging reactions, such as oxidation of methane and oxidation of water in artificial photosynthesis. The subject of supported metal pair-site catalysts is in its infancy, facing challenges in (a) precise synthesis, (b) structure determination at the atomic scale, and (c) stabilization in reactive atmospheres. In this Perspective, we summarize key characteristics of molecular and enzymatic catalysts that incorporate neighboring metal centers and build on this foundation to assess the emerging literature of metal pair-site catalysts on various supports. The supported catalysts include those synthesized by anchoring molecular dinuclear precursors to support surfaces and those synthesized by selective formation of dinuclear surface species from mononuclear surface species. Examples of metals in this class are rhodium and iridium, and examples of supports are MgO and Fe 2 O 3 . We summarize characterization of these materials by electron microscopy and spectroscopy, emphasizing atomic-resolution aberration-corrected scanning transmission electron microscopy and spectroscopies that provide atomic-scale structural information and allow characterization of functioning catalysts, especially X-ray absorption spectroscopy. Finally, we list some opportunities for research, including suggestions that might lead to structurally well-defined supported metal pair-sites with new catalytic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Electronic Structure of Atomically Dispersed Supported Iridium Catalyst Controls Iridium Aggregation

Supported iridium complexes, Ir(C 2 H 4 ) 2 /support, were characterized by X-ray absorption spectroscopy during a temperature ramp to 120 °C in flowing H 2 . Iridium in complexes bonded to weak and moderate electron-donor supports, SiO 2 and γ-Al 2 O 3 , underwent aggregation, forming nanoparticles and clusters, respectively. When the support was a strong electron-donor (MgO), iridium remained site-isolated. Density functional theory calculations confirm the dependence of iridium–support bond strength on the support’s electron-donor character. Coating the SiO 2 -supported complexes with 1-n-ethyl-3-methyl-imidazolium acetate enhanced electron density on the iridium, hindering its aggregation. Finally, these results demonstrate opportunities for stabilizing atomically dispersed supported noble metals under reducing conditions by choice of support/ionic liquid sheath combinations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2017

NASA Weather Support 2017

In the mid to late 1980's, as NASA was studying ways to improve weather forecasting capabilities to reduce excessive weather launch delays and to reduce excessive weather Launch Commit Criteria (LCC) waivers, the Challenger Accident occurred and the AC-67 Mishap occurred.[1] NASA and USAF weather personnel had advance knowledge of extremely high levels of weather hazards that ultimately caused or contributed to both of these accidents. In both cases, key knowledge of the risks posed by violations of weather LCC was not in the possession of final decision makers on the launch teams. In addition to convening the mishap boards for these two lost missions, NASA convened expert meteorological boards focusing on weather support. These meteorological boards recommended the development of a dedicated organization with the highest levels of weather expertise and influence to support all of American spaceflight. NASA immediately established the Weather Support Office (WSO) in the Office of Space Flight (OSF), and in coordination with the United Stated Air Force (USAF), initiated an overhaul of the organization and an improvement in technology used for weather support as recommended. Soon after, the USAF established a senior civilian Launch Weather Officer (LWO) position to provide meteorological support and continuity of weather expertise and knowledge over time. The Applied Meteorology Unit (AMU) was established by NASA, USAF, and the National Weather Service to support initiatives to place new tools and methods into an operational status. At the end of the Shuttle Program, after several weather office reorganizations, the WSO function had been assigned to a weather branch at Kennedy Space Center (KSC). This branch was dismantled in steps due to further reorganization, loss of key personnel, and loss of budget line authority. NASA is facing the loss of sufficient expertise and leadership required to provide current levels of weather support. The recommendation proposed herein is to re-establish the WSO under a high level office, with funding set at about the same levels as today, with a revitalized charter and focus to allow for the WSO to operate as originally intended.

lessons learned↗

NASA NTRS2019

Controls and Automation Research in Space Life Support

A highly controlled and automated life support system has long been a NASA goal. It is usually assumed that life support for future long duration missions will use physical/chemical recycling systems that substantially close the oxygen and water circulation loops. Such a tightly coupled life support system has been thought to require an overall supervisory control system to minimize crew operation and maintenance activities. The International Space Station (ISS) Environmental Control and Life Support System (ECLSS) was at first expected to have supervisory control and automation. After this was found infeasible during the design of the ISS ECLSS in the early 1990's, it was then expected that the ISS or future mission systems would be upgraded to meet the original expectations. Since then NASA has extensively researched life support system controls and automation. Automation and Artificial Intelligence (AI) have gone through several cycles of enthusiasm and neglect before their recent great achievements, and NASA life support interest has similarly varied. Since the ISS ECLSS was launched, its on-board operational problems have led NASA to deemphasize system level controls and automation in favor of improving subsystem reliability and maintainability. Recent work has investigated supervisory control for a system similar to the ISS ECLSS. This paper reviews past planning and work on the supervisory control of closed, integrated physical/chemical life support systems similar to the ISS ECLSS and its precursors dating back to the 1960's.

life support↗

NASA NTRSDate not supplied

A Decision Support System for Extravehicular Operations Under Significant Communication Latency

Within the next few decades, humanity hopes to perform extravehicular activities (EVAs) on the surface of Mars; however, several technical and operational challenges must first be overcome. Foremost among these challenges is managing a significant two-way communication latency between Earth and Mars. Current and historical paradigms of EVA operations have required near-real-time communication between the crewmember(s) performing an EVA and an Earth-based mission control. Next-generation operational paradigms for supporting deep space exploration will necessitate a distributed decision authority system, including delayed Earth-based mission control, the on-planet extravehicular crewmember(s), and intermediate mission support from intravehicular crewmember(s) within real-time communication range. This latter group is of particular interest: they must provide operations support without the plentiful resources available to mission control on Earth. For this purpose, NASA is developing the Personalized EVA Informatics and Decision Support (PersEIDS) software platform. PersEIDS is designed to bolster operator situational awareness and offload operator workload by automating the tracking and projection of consumables usage over an EVA timeline, providing real-time probabilistic safety assessments of an EVA timeline given consumables constraints, and recommending alternative EVA timeline(s) when the active timeline is not expected to be completed under consumables limits. The PersEIDS concept of operations, use cases, and models will be presented. A limited version of PersEIDS was demonstrated during a three-day-long study where each day a roughly four-hour-long simulated Martian EVA was performed in virtual reality at the NASA Johnson Space Center. The first day was a control trial without PersEIDS support; the second and third days represented different levels of decision support provided by PersEIDS to the intravehicular crewmember acting as mission control. With PersEIDS support, the IV crewmember was able to manage the mission to completion faster and with more remaining consumables; however, additional testing is required to understand confounding factors, e.g. training bias.

Mars↗

NASA NTRSDate not supplied

A Decision Support System for Extravehicular Operations Under Significant Communication Latency

Humanity hopes to perform extravehicular activities (EVAs) on the surface of Mars; however, several technical and operational challenges must first be overcome. Foremost among these challenges is managing a significant communication latency between Earth and Mars. Current and historical paradigms of EVA operations have required near-real-time communication between the crewmember(s) and Earth-based mission control. Nextgeneration operational paradigms for supporting deep space exploration will necessitate a distributed decision authority system, including delayed Earth-based mission control, the onplanet extravehicular crewmember(s), and intermediate mission support from intravehicular (IV) crewmember(s) within real-time communication range. This latter group is of particular interest: they must provide operations support without the plentiful resources available to mission control on Earth. Thus, NASA is developing the Personalized EVA Informatics and Decision Support (PersEIDS) software platform. PersEIDS is designed to bolster operator situational awareness and offload operator workload by automatically tracking and projecting consumables usage over an EVA timeline, providing real-time probabilistic safety assessments and recommending alternative EVA timeline(s) when the active timeline is not expected to be completed under consumables limits. The PersEIDS concept of operations, use cases, and models will be presented. A limited version of PersEIDS was demonstrated during a three-day-long study where each day a roughly four-hour-long simulated Martian EVA was performed in virtual reality at the NASA Johnson Space Center. The first day was a control trial without PersEIDS support; the second and third days represented different levels of decision support provided by PersEIDS to the IV crewmember acting as mission control. With PersEIDS support, the IV crewmember was able to manage the mission to completion faster and with more remaining consumables; however, additional testing is required to understand confounding factors, e.g., training bias.

Mars↗

NASA NTRSDate not supplied

PersEIDS: A Biomedical Decision Support System for Extravehicular Operations Under Significant Communication Latency

Humanity hopes to perform extravehicular activities (EVAs) on the surface of Mars; however, several technical and operational challenges must first be overcome. Foremost among these challenges is managing a significant communication latency between Earth and Mars. Current and historical paradigms of EVA operations have required near-real-time communication between the crewmember(s) and Earth-based mission control. Nextgeneration operational paradigms for supporting deep space exploration will necessitate a distributed decision authority system, including delayed Earth-based mission control, the onplanet extravehicular crewmember(s), and intermediate mission support from intravehicular (IV) crewmember(s) within real-time communication range. This latter group is of particular interest: they must provide operations support without the plentiful resources available to mission control on Earth. Thus, NASA is developing the Personalized EVA Informatics and Decision Support (PersEIDS) software platform. PersEIDS is designed to bolster operator situational awareness and offload operator workload by automatically tracking and projecting consumables usage over an EVA timeline, providing real-time probabilistic safety assessments and recommending alternative EVA timeline(s) when the active timeline is not expected to be completed under consumables limits. The PersEIDS concept of operations, use cases, and models will be presented. A limited version of PersEIDS was demonstrated during a three-day-long study where each day a roughly four-hour-long simulated Martian EVA was performed in virtual reality at the NASA Johnson Space Center. The first day was a control trial without PersEIDS support; the second and third days represented different levels of decision support provided by PersEIDS to the IV crewmember acting as mission control. With PersEIDS support, the IV crewmember was able to manage the mission to completion faster and with more remaining consumables; however, additional testing is required to understand confounding factors, e.g., training bias.

Mars↗

NASA NTRSDate not supplied

Modeling Logistics and Supportability for Crewed Missions Beyond Low Earth Orbit

NASA’s future missions aim to establish a sustained human presence on the lunar surface and send humans to Mars. These missions will send crews farther from home than previous missions, limiting the opportunities for resupply missions. Additionally, the use of multiple launches and reusable elements will increase mission and campaign complexity. Logistics and supportability analysis evaluates the link between mission and system characteristics and key metrics such as logistics and spares mass and volume, crew time, and risk. As missions become increasingly complex and crews are logistically isolated for longer periods of time, logistics and supportability will become more powerful drivers of risk and cost and, therefore, more important considerations during system and mission development. When logistics and supportability are considered from the beginning of system and mission development, opportunities arise to create more efficient, lower-risk systems. Design choices made without detailed consideration of logistics and supportability have the potential to result in greater risks and increased costs as all options may not have been analyzed. This paper provides an overview of a methodology used for space mission logistics and supportability analysis, including key metrics, assumptions, and required inputs. Example applications of this methodology to explore the impacts of system architecture, dormancy, and synergies between lunar and Mars missions are also presented. Conducting these holistic analyses enables informed decision-making for mission planning and system design, which can help mitigate the risk of loss of mission, vehicle, or crew. Using the knowledge of historical missions, experiences gained on the lunar surface, and logistics and supportability analyses, NASA can examine and optimize supportability characteristics for safer and more effective operations for future lunar and Mars missions.

Supportability↗

NASA NTRSDate not supplied

Modeling Logistics and Supportability for Crewed Missions Beyond Low Earth Orbit

NASA’s future missions aim to establish a sustained human presence on the lunar surface and send humans to Mars. These missions will send crews farther from home than previous missions, limiting the opportunities for resupply missions. Additionally, the use of multiple launches and reusable elements will increase mission and campaign complexity. Logistics and supportability analysis evaluates the link between mission and system characteristics and key metrics such as logistics and spares mass and volume, crew time, and risk. As missions become increasingly complex and crews are logistically isolated for longer periods of time, logistics and supportability will become more powerful drivers of risk and cost and, therefore, more important considerations during system and mission development. When logistics and supportability are considered from the beginning of system and mission development, opportunities arise to create more efficient, lower-risk systems. Design choices made without detailed consideration of logistics and supportability have the potential to result in greater risks and increased costs as all options may not have been analyzed. This paper provides an overview of a methodology used for space mission logistics and supportability analysis, including key metrics, assumptions, and required inputs. Example applications of this methodology to explore the impacts of system architecture, dormancy, and synergies between lunar and Mars missions are also presented. Conducting these holistic analyses enables informed decision-making for mission planning and system design, which can help mitigate the risk of loss of mission, vehicle, or crew. Using the knowledge of historical missions, experiences gained on the lunar surface, and logistics and supportability analyses, NASA can examine and optimize supportability characteristics for safer and more effective operations for future lunar and Mars missions.

Supportability↗

DOE OSTI2022

Direct non-oxidative methane coupling on vitreous silica supported iron catalysts

Direct non-oxidative methane coupling (NMC) is one of the promising pathways for methane upgrading into value-added olefin and aromatic hydrocarbons. The silica-supported iron (i.e., Fe/SiO 2 ) catalyst has been reported effective for NMC, but the effects of silica support on the catalyst property and NMC performance have rarely been explored. Here, in this work, we prepared a vitreous silica-supported iron (Fe/SiO 2 -V) catalyst by flame fusion of a mixture of quartz silica and fayalite. The physicochemical properties and NMC performance of the as-prepared catalysts were measured. Compared to crystalline cristobalite support in Fe/SiO 2 catalyst that has been studied previously, vitreous silica support has disordered Si-O bonds and structural defects, enabling better iron dispersion and more vital metal-support interaction. The as-prepared Fe/SiO 2 -V catalyst had a shorter induction period in methane activation and lower coke yield in NMC. The increase in iron concentration in Fe/SiO 2 -V catalysts elongated the catalyst induction period and promoted aromatics and coke formation. The coke type of the spent Fe/SiO 2 -V catalyst is more uniform than the cristobalite-supported iron catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

The effect of silica oxide support on the catalytic activity of nickel-molybdenum bimetallic catalyst toward ethanol steam reforming for hydrogen production

This work investigates the effects of molybdenum promoter and silica oxide (SiO 2 ) support morphology on the ethanol steam reforming (ESR) performance of Nickel-Molybdenum (NiMo) bimetallic catalysts. Ordered mesoporous SiO 2 (SBA-15) and commercial SiO 2 supports were used as the oxide support materials. The synthesized catalysts were prepared via the wet impregnation method and characterized via XRD, H 2 -TPR, BET, FTIR, and Raman techniques. This study shows that NiMo bimetallic catalyst supported on SBA-15 has superior catalytic activity and better coking resistance at an intermediate temperature of 600 ⁰C than commercial SiO 2 supported catalysts. The presence of a uniform mesoporous structure of SBA-15 with an average pore diameter of ~ 2 nm can obstruct the carbon formation, leading to improved coking resistance. The catalytic enhancement of NiMo bimetallic catalysts toward ESR can also be linked to the ability of Mo promoter in enhancing the interaction between NiMo nanoparticles and SiO 2 support materials and restraining agglomeration of Ni nanoparticles, which results in further improvement of NiMo nanoparticle dispersion and inhibit its sintering. The NiMo bimetallic catalysts supported on SBA-15 illustrated the high H 2 yield of ~ 54% and carbon conversion of ~ 89% with the excellent stability for ESR performed at 600 ⁰C and the steam-to-carbon ratio of 2 over 65 hours.

25 ENERGY STORAGE↗

DOE OSTI2023

Low-Energy Ion Scattering Intensities from Supported Nanoparticles: The Spherical Cap Model

Supported nanoparticles are of great importance to many technologies like fuel processing and chemical synthesis using catalysts and electrocatalysts, energy storage and generation using fuel cells and batteries, electrochemistry, magnetic information storage, and more. Low-energy ion scattering spectroscopy (LEIS) with noble gas ions like He+ is a powerful tool for the characterization of nanoparticles dispersed across flat support surfaces due to its ability to probe the elemental composition in the topmost atomic layer of a surface, providing quantitative information regarding the size and number density of nanoparticles. In this work, we present a derivation of the LEIS intensities expected from nanoparticles and the support material as a function of the average particle size, their number per unit area, and their contact angle with the support when modeled as spherical caps of the nanoparticle material dispersed over the surface of a flat support. The model assumes that the ion intensities are determined only by the physical blocking of linear ion trajectories and independent of the tilt angle of the local surface relative to the incident and scattered ion directions, an assumption we support by quantitative modeling of published data which tested tilt-angle effects. The model is a generalization to arbitrary contact angles of the hemispherical cap model, which assumes 90° contact angle and has been widely used to model spectroscopic signals in LEIS (and also in Auger and photoelectron spectroscopies) during nanoparticle growth. Here, this new model quantitatively reveals how LEIS signals are sensitive not only to the diameter and number density of the nanoparticle but also to their contact angle (or height/diameter ratio). With the use of additional data (e.g., from microscopy or adsorption microcalorimetry), the model presented here will enable more accurate determination of the average size, shape, and number density of supported nanoparticles based on LEIS intensity measurements.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2020

Hybrid-Supported Bilayers Formed with Mixed-Charge Surfactants on C 18 -Functionalized Silica Surfaces

Mixtures of cationic-anionic surfactants have been demonstrated to spontaneously form ordered monolayers at hydrophobic-hydrophilic boundaries including air-water and oil-water interfaces. Here, confocal Raman microscopy is used to investigate the structure of hybrid-supported surfactant bilayers (HSSBs) formed by deposition of a distal leaflet of mixed cationic-anionic surfactants onto a proximal leaflet of n-alkane (C 18 ) chains on the interior surfaces of chromatographic silica particles. The surface coverage of the two surfactants in a hybrid bilayer was determined from carbon analysis and the relative Raman scattering of their respective head-groups. Within the measurement uncertainty, the stoichiometric ratio of the two surfactants is one-to-one, equivalent to mixed-charge-surfactant monolayers at air-water and oil-water interfaces and consistent with the role of the head-group electrostatic interactions in their formation. When self-assembled on the hydrophobic surface, pairs of oppositely-charged n-alkyl-chain surfactants resemble a phospholipid (phosphati¬dylcholine) molecule, with its zwitterionic head group and two hydrophobic acyl-chain tails. Indeed, the structure of these hybrid-supported surfactant bilayers on C 18 -modified silica surfaces is similar to that of hybrid-supported lipid bilayers (HSLBs) on the same supports, but with denser and more-ordered n-alkyl chains. Hybrid-supported surfactant bilayers exhibit a melting phase transition (gel to liquid-crystalline phase) with structural and energetic characteristics similar to hybrid-supported bilayers prepared from a zwitterionic phospholipid of the same alkyl chain length. These mixed-charge surfactants on n-alkane modified silica are stable in water over time (months), results that suggest the potential use of these hybrid bilayers for generating supported lipid bilayer-like surfaces or for separation applications.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Studying the Durability of Molybdenum Carbide Aerogel as an Electrocatalyst Support for Proton Exchange Membrane Fuel Cells

Carbon-supported platinum nanoparticles (Pt/C) are currently the state-of-the-art catalyst in proton exchange membrane fuel cells (PEMFCs). Unfortunately, the carbon support lacks the ability to stabilize the metal catalyst, as platinum tends to dissolve and agglomerate, significantly compromising the durability. Herein, we synthesized a ceramic material, molybdenum carbide aerogel (MCAG), and utilized it as a Pt support for PEMFCs, as an alternative for conventional carbon supports. N 2 adsorption and XRD analysis showed that the MCAG possesses a combination of high porosity and a well-defined ceramic crystalline structure. The Pt/MCAG system was studied for its electrocatalytic activity toward ORR in a half-cell and demonstrated satisfactory reaction kinetics and electrochemical active surface area, comparable to the commercial Pt/C. For durability examination, an accelerated stress test (AST) in a single cell was conducted with the Pt/MCAG catalyst at the cathode, following the U.S. DOE electrocatalyst AST protocol. Intermediate polarization curves and cyclic voltammograms were recorded over the course of the AST to monitor the aging process. The results indicated that the MCAG support exhibited superior durability in long-term fuel cell operation compared to a carbon support. The Pt/MCAG system demonstrated stable behavior during the progressive stages of the AST, retaining more than 50% of its initial performance by the end of the test, whereas carbon-supported Pt preserved only 30%.

25 ENERGY STORAGE↗