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At least 739 records · Page 41

Structure analysis of supported disordered molybdenum oxides using pair distribution function analysis and automated cluster modelling

Molybdenum oxides and sulfides on various low-cost high-surface-area supports are excellent catalysts for several industrially relevant reactions. The surface layer structure of these materials is, however, difficult to characterize due to small and disordered MoO x domains. Here, it is shown how X-ray total scattering can be applied to gain insights into the structure through differential pair distribution function (d-PDF) analysis, where the scattering signal from the support material is subtracted to obtain structural information on the supported structure. MoO x catalysts supported on alumina nanoparticles and on zeolites are investigated, and it is shown that the structure of the hydrated molybdenum oxide layer is closely related to that of disordered and polydisperse polyoxometalates. By analysing the PDFs with a large number of automatically generated cluster structures, which are constructed in an iterative manner from known polyoxometalate clusters, information is derived on the structural motifs in supported MoO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aging Effect Analysis of PV Inverter Semiconductors for Ancillary Services Support

PV inverters can provide reactive power while generating active power. An ongoing microgrid implementation at Duke Energy actively engages non-utility PVs to generate/absorb reactive power in support of ancillary services to increase microgrid resiliency during extreme events. PV systems are requested to provide reactive power support: 1) in response to grid voltage variation to better regulate the local voltage; or 2) in response to utility incentives, such as following Transactive Energy System (TES) incentives. However, providing ancillary services might shorten the lifetime expectation of PV inverter semiconductors. This paper summarizes the potential impacts on a PV inverter semiconductor's lifetime when providing ancillary services. The analysis presented in this research work shows that providing reactive power support will increase the mean junction temperature and the junction temperature variation of the inverter diodes. This increased junction temperature will eventually lead to shorter diode lifetime. The lifetime estimation of semiconductors is briefly reviewed. The power losses of PV inverter semiconductors are derived as a support analysis to the junction temperature calculation. In addition, the impact of the filtering inductor on the semiconductor current distribution is discussed. The theoretical analysis presented in this research work is supported by simulation results.

14 SOLAR ENERGY↗

Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only in the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. As a result, with the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Towards Next-Generation Urban Decision Support Systems through AI-Powered Construction of Scientific Ontology Using Large Language Models—A Case in Optimizing Intermodal Freight Transportation

The incorporation of Artificial Intelligence (AI) models into various optimization systems is on the rise. However, addressing complex urban and environmental management challenges often demands deep expertise in domain science and informatics. This expertise is essential for deriving data and simulation-driven insights that support informed decision-making. In this context, we investigate the potential of leveraging the pre-trained Large Language Models (LLMs) to create knowledge representations for supporting operations research. By adopting ChatGPT-4 API as the reasoning core, we outline an applied workflow that encompasses natural language processing, Methontology-based prompt tuning, and Generative Pre-trained Transformer (GPT), to automate the construction of scenario-based ontologies using existing research articles and technical manuals of urban datasets and simulations. From these ontologies, knowledge graphs can be derived using widely adopted formats and protocols, guiding various tasks towards data-informed decision support. The performance of our methodology is evaluated through a comparative analysis that contrasts our AI-generated ontology with the widely recognized pizza ontology, commonly used in tutorials for popular ontology software. We conclude with a real-world case study on optimizing the complex system of multi-modal freight transportation. Our approach advances urban decision support systems by enhancing data and metadata modeling, improving data integration and simulation coupling, and guiding the development of decision support strategies and essential software components.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗

Don't Trust a Management Metric, Especially in Life Support

Goodhart's law states that metrics do not work. Metrics become distorted when used and they deflect effort away from more important goals. These well-known and unavoidable problems occurred when the closure and system mass metrics were used to manage life support research. The intent of life support research should be to develop flyable, operable, reliable systems, not merely to increase life support system closure or to reduce its total mass. It would be better to design life support systems to meet the anticipated mission requirements and user needs. Substituting the metrics of closure and total mass for these goals seems to have led life support research to solve the wrong problems.

life support↗

Streamlining Pre-Launch Support for Missions with Highly Variable Trajectories

As the Goddard Space Flight Center's (GSFC) Flight Dynamics Facility (FDF) continues to ensure mission success in support of Human Space Flight (HSF) and Launch Vehicle (LV) missions, it continues to improve on different areas of mission support. The FDF processes numerous different types of trajectory profiles, and, for each trajectory, the FDF provides multiple acquisition data vectors to the Space Network (SN) White Sands Complex (WSC) for further processing and uplinking to the SN's Tracking and Data Relay Satellites (TDRSs), tracking the vehicle and maintaining communications throughout required support. Some trajectories target a specific orbit plane through Right Ascension of the Ascending Node (RAAN), or yaw, steering, which can yield to high variability across the launch window. Because of this, there can be a large number of trajectory profiles to process and generate acquisition data for that ensure TDRS is accurately pointing to the launch vehicle. Processing many trajectory profiles by FDF and WSC increases the complexity and level of effort associated with support. FDF employs a legacy boundary on the range difference between trajectories, which determines the number of discrete trajectory cases required to maintain communication with TDRS over the full launch window. An analysis was performed to determine a new boundary, taking into consideration current support requirements. The results show the boundary can be expanded beyond the currently employed legacy value without an impact on communication. In doing so, the number of trajectory profiles processed can be reduced, reducing the complexity and level of effort required, with no impact to mission safety.

Flight Operations↗

Market Survey 2020: Commercial Clinical Decision Support Systems and Wellness Tools

For long-duration, deep space exploration missions, current methods for managing and supporting crew health and medical conditions will be unsuitable. Communication and data transmission lags will necessitate the use of a sophisticated clinical decision support system (CDSS) that will tailor diagnosis and treatment guidance that is context-sensitive for anticipated astronaut health, wellness, and medical conditions. A variety of clinical decision support (CDS) and wellness tools (WT) are currently available in the commercial market and a broad-brush survey of this market can provide an initial impression of the current state of the art which, in turn, can inform the roadmap of NASA deep space CDSS development and associated requirements. Such a survey was undertaken during the first six months of 2020 using directed convenience sampling to obtain information provided by vendors on their websites; both commercially available CDS and WT (such as those used to track and monitor nutrition, exercise, and sleep) were included. Areas assessed were item type (e.g., software/application, device); primary purpose of the item (e.g., diagnostic support, nutrition tracking); additional purposes (if any); reported features, capabilities, and functionality; setting of use (e.g., inpatient, outpatient); intended user (e.g., clinician, patient); location and sources of data/information used or produced by the item; integration with patient electronic health record (EHR); compliance with interoperability ontologies and standards (e.g., Health Level 7 [HL7], Systematized Nomenclature of Medicine – Clinical Terminology [SNOMED-CT]); and whether the item is knowledge-based (derived from research findings) or non-knowledge-based (derived through artificial intelligence, machine learning, advanced probability and statistics), among others. Ninety-seven (97) vendor websites describing 196 CDS and 73 WT (269 total) were reviewed and coded. The primary purpose of the majority of CDS reviewed is diagnosis or diagnosis/treatment/drug decision support—targeted for clinician use— and the primary purpose of the majority of WT reviewed is the monitoring of different health metrics, most often through the use of a biosensor device (e.g., blood pressure)—targeted for patient use. Very few CDS or WT appear to comply with major international interoperability standards or can be integrated with a patient’s EHR data. None consider contextual factors, such as conditions of the physical environment (e.g., CO2 levels). The majority of CDS and WT reviewed are non-knowledge, cloud- or web-based applications or software. Forty-three (43) major findings were identified and the implications those findings have for NASA will be discussed. Example major findings include: CDS-WT capabilities range from diagnosis to treatment applications, CDS-WT may be wearable or non-wearable and are technologically advanced and only a few CDS-WT tools referenced compliance to ensure interoperability, among other findings. Recommendations will also be offered that will help to address ExMC Gap, Medical-701: Enhance medical capabilities within an exploration medical system.

market survey↗

NASA Environmental Control and Life Support Technology Development for Exploration: 2020 to 2021 Overview

This PowerPoint presentation supports the following paper submission's abstract (STRIVES 20210015025). This paper provides an overview of NASA supported activities developing Environmental Control and Life Support (ECLSS) technologies in the following capability areas: life support, environmental monitoring, fire safety, and logistics. NASA has been refining technology needs for deep space missions including Gateway, lunar surface, Mars transit, and Mars surface missions. Validating technologies in relevant environments, both in low earth orbit (LEO) and ground tests is critical in understanding technology performance and long duration performance. On-orbit and ground tests inform NASA’s technology decisions to fill exploration gaps. NASA has multiple technology projects across the technology readiness spectrum with potential to fill or partially fill exploration gaps. For each capability area, this paper will describe select capability gaps, NASA technology project maturation over the past year, and key performance parameters (KPPs). KPPs are evolving but they still provide a useful measure in communicating progress and identifying development needs to fill exploration gaps. The intent is to provide a very high-level overview describing the projects that are supporting gap closure and provide references to additional technical details, progress, and KPPs.

Life Support↗

BETO 2021 Peer Review - Strategic Analysis Support WBS 4.1.1.30

Strategic Analysis Support. The objective of the NREL strategic support project is to provide sound, unbiased, and consistent analyses to inform the strategic direction of the DOE BETO office. This project addresses key technological questions, provides critical data needed to inform strategy, and highlights barriers, gaps and data needs in support of the DOE BETO's mission to improve the affordability of bio-based fuels and products. This task employs various quantitative (techno-economic analysis, TEA) and qualitative (gap analysis) approaches to allow for direct comparisons of biomass conversion technologies across a wide slate of processing platforms and products. Furthermore, this project develops and utilizes novel analyses beyond traditional biorefinery focused TEA/LCAs to identify both technical (e.g., in sustainable design) and non-technical (e.g., in value proposition) barriers, as well as to outline mitigation strategies and R&D needs for emerging technologies. Additionally, the project is tasked with evaluating drivers that support the growing bio-economy, which is achieved by the development and public release of tools to advance the understanding and facilitate comparisons of socio-economic impacts along the supply chain. Critical to the success of this project is the development of defensible methodologies, analyses, and tools that are publicly available to support stakeholders and bioeconomy growth. To develop such high-quality analyses, the biggest challenge to this project, as with most analysis focused projects, is the availability and reliability of the underlying data. Therefore, the project team works extensively with key stakeholders (e.g., policy makers, bioenergy technology developers, and investors) in developing and reviewing the results of these analyses to overcome this challenge. Any remaining uncertainties associated with the analysis efforts are clearly defined and quantified.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

NASA's Advanced Life Support Systems Human-Rated Test Facility

Future NASA missions to explore the solar system will be long-duration missions, requiring human life support systems which must operate with very high reliability over long periods of time. Such systems must be highly regenerative, requiring minimum resupply, to enable the crews to be largely self-sufficient. These regenerative life support systems will use a combination of higher plants, microorganisms, and physicochemical processes to recycle air and water, produce food, and process wastes. A key step in the development of these systems is establishment of a human-rated test facility specifically tailored to evaluation of closed, regenerative life supports systems--one in which long-duration, large-scale testing involving human test crews can be performed. Construction of such a facility, the Advanced Life Support Program's (ALS) Human-Rated Test Facility (HRTF), has begun at NASA's Johnson Space Center, and definition of systems and development of initial outfitting concepts for the facility are underway. This paper will provide an overview of the HRTF project plan, an explanation of baseline configurations, and descriptive illustrations of facility outfitting concepts.

NASA Discipline Number 61-10↗

Bioregenerative life support systems for long-term space habitation: a conceptual approach

Life support systems represent one of the most critical aspects of human space exploration. Future long-term missions such as the establishment of human-tended Lunar and Martian bases require closed life support systems. A conceptual approach to an Engineered Closed/Controlled EcoSystem incorporating bioregenerative capabilities by integrating humans, plants, and waste management processes is presented. The integration of physical/chemical and biological waste treatment processes is suitable for supporting plant growth through hydroponics and materially closing the human and plant metabolic loops. This conceptual design separates wastes into individual loops for treatment according to the specific metabolic needs of humans and plants. The means through which an integrated Engineered Closed/Controlled EcoSystem meets the life support objectives of long-term space habitation are summarized.

Non-NASA Center↗

Monitoring Structural and Electronic Changes of Supported Metal Catalysts Using Combined X‐Ray Techniques

Supported metal nanoparticle catalysts have become increasingly crucial for many catalytic applications. However, long-term catalyst stability remains a problem due to catalyst deactivation caused by coke formation and sintering. The deposition of a thin overcoating via atomic layer deposition (ALD) onto metal-supported nanoparticles has shown to greatly inhibit catalyst deactivation. This work utilizes a model catalyst system comprised of Pt nanoparticles supported on Al 2 O 3 to demonstrate the effect of an atomically thin overcoating on supported metal nanoparticles. Continuous operando small-angle X-ray scattering (SAXS) and X-ray absorption near edge spectroscopy (XANES) monitor structural and electronic changes to the catalyst and overcoating during calcination. SAXS data fitting reveals the formation of nanopores in the overcoating at high temperatures, while XANES monitors the oxidation state of the Pt catalyst. Herein, the usefulness of combined X-ray techniques is demonstrated to characterize supported metal catalysts to further understanding of the synergistic effects of the ALD overcoating to aid in the design of new catalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring the Cooperative Acid-Base Effects in Silica-Supported Amine Catalysts: Applications in the Continuous Gas-Phase Self-Condensation of n -Butanal

A highly efficient solid-base organocatalyst for the gas-phase aldol self-condensation of n -butanal to 2-ethylhexenal was developed by grafting site-isolated amines on tailored silica surfaces. The catalytic activity depends largely on the nature of amine species, the surface concentration of amine and silanol groups, and the spatial separation between the silanol and amine groups. In situ FTIR measurements demonstrated that the formation of nucleophilic enamines leads to the enhanced catalytic activity of secondary amine catalysts, whereas the formation of imines (stable up to 473 K) leads to the low activity observed for silica-supported primary amines. Blocking the silanol groups on the silica support by silylation or cofeeding water into the reaction stream drastically decreased the reaction rates, demonstrating that weaker acidic silanol groups participate cooperatively with the amine groups to catalyze the condensation reaction. This work demonstrates that the spatial separation of the weakly acidic silanols and amines can be tuned by the controlled dehydration of the supporting silica and by varying the linker length of the amine organosilane precursor used to graft the amine to the support surface. A mechanism for aldol condensation was proposed and then analyzed by DFT calculations. DFT analysis of the reaction pathway suggested that the rate-limiting step in aldol condensation is carbon-carbon bond formation, which is consistent with the observed kinetics. The calculated apparent activation barrier agrees reasonably with that measured experimentally. Secondary amines come first: A solid-base organocatalyst achieved by grafting amines onto silica surfaces is applied to the gas-phase aldol self-condensation of n-butanal to 2-ethylhexenal. Silica-supported secondary amine catalysts demonstrate a much higher catalytic activity than the primary amine analogues, owing to the respective formation of enamines as shown by in situ FTIR analysis. The reaction pathway is analyzed by DFT calculations.

acidity↗

Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes

It has been a long-standing goal to find alternative, cost effective catalysts for oxygen reduction reaction (ORR) in fuel cells. Molecular complexes capable of efficiently catalyzing ORR, when supported on a conducting solid surface could provide interesting hybrid materials combining the best of homogeneous and heterogeneous catalysis. Here, we utilize density functional theory to study the ORR activity of molecular (unsupported) and gold supported 3d metal (II)-porphycenes (MPc). All the 3d metal-porphycenes adsorb strongly on the Au(111) support with negative free energy of formation ranging from 1.0–3.0 eV while solvation lowers the energy of molecular MPc by only 0.5 eV compared to the gas phase. These indicate that the 3d MPc are stable and anchored firmly to the gold surface under ORR conditions. Based on our analysis, the gold support enhances the ORR activity in some of the examined MPc systems. We find that the molecular MnPc and FePc are the best ORR electrocatalysts with theoretical overpotentials of 0.44 V and 0.36 V. Thus, this work highlights the important role of the support in preserving/increasing the activity of molecular catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Highly Selective Support for CO Hydrogenation to Light Olefins with Partially Passivated Iron Catalysts

To rule out disturbances from water=soluble efficient promoters (e. g., K 2 O or combination of S/Na), a simplified iron/support catalyst system was employed to investigate novel supports for the catalytic conversion of syngas (CO+H 2 ) to light olefins (FTO). A series of supports with nominal compositions of ZnAl 2 O 4 ∙ x Al 2 O 3 ( x =1, 2, 3) were prepared by coprecipitation and subsequent high temperature calcination at 1200 °C for 24 h to generate partially passivated ZnAl 2 O 4 and Al 2 O 3 phases, through which each formed component of a catalyst may minimize interactions among them and exhibit unique activity. Iron catalysts were prepared by incipient wetness of iron salts over these supports. At a total pressure of ca. 20 bar and a CO conversion of 35 %, a catalyst with a nominal composition of 15 %Fe/85 %(ZnAl 2 O 4 ∙ 3Al 2 O 3 ) exhibits a surprising C 2 = -C 4 = hydrocarbon distribution of 58 %, which reaches a huge increase by almost 100 % in comparison with iron catalysts over regular supports (e. g., carbon, gamma-Al 2 O 3 , etc.). This catalyst demonstrates the 1200 °C passivated ZnAl 2 O 4 ∙ 3Al 2 O 3 as probably the most selective support material for iron-based FTO catalysts. At CO conversion of 35 %, the contents of ethylene in C 2 , propylene in C 3 , and butylene in C 4 products achieve extraordinary values of 82%, 92%, and 91%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bidentate N‐based Ligands for Highly Reusable, Ligand‐coordinated, Supported Pt Hydrosilylation Catalysts

Abstract A significant challenge in designing supported metal‐ligand catalysts for solution‐phase reactions is the stabilization of the metal active sites against leaching into solution. Here, we examine alkene hydrosilylation reactions as model systems to improve the stability of highly dispersed Pt using a metal‐ligand coordination strategy on high surface area oxide supports. By evaluating a series of bidentate N‐based ligands, we demonstrate several design strategies to improve stability of the highly dispersed Pt 2+ centers against leaching, while maintaining a high level of catalytic activity, selectivity, and recyclability for alkene hydrosilylation batch reactions under mild conditions. These involve a bi‐functional approach to ligand design, which considers interaction to the support and a well‐defined coordination environment for the metal active site. Three strategies are reported: modifying ligands for stronger interaction with oxide surfaces, mixing ligands, and pre‐depositing an “anchoring ligand” to the support before loading the metal‐ligand catalyst. Each of these is successful in enhancing Pt recyclability. Particularly, two Pt‐phenanthroline catalysts exhibit excellent reusability for multiple batch reaction cycles, due to high stability of the active Pt species. Addressing the active site leaching problem significantly enhances the utility of ligand‐coordinated supported metal catalysts as highly stable and selective catalysts for solution‐phase reactions.

Chen, Linxiao↗

CO 2 Oxidative Ethane Dehydrogenation on CeO 2 /SiO 2 ‐Supported NiFe 3 Catalysts

CO 2 -assisted oxidative dehydrogenation of ethane is a sustainable alternative to steam cracking for ethylene production. In this study, a series of CeO 2 on SiO 2 supported NiFe 3 catalysts were synthesized by incipient wetness impregnation and tested for oxidative dehydrogenation performance. The CeO 2 /SiO 2 supported catalysts with high weight loading of CeO 2 (50%–75%) provided higher activity than the lower CeO 2 (0%–25%) loaded catalysts (with ethylene production rates of 0.62–0.98 µmol/g cat /s and 0.19–0.3 µmol/g cat /s, respectively) while maintaining high ethylene selectivity (43%–45%). In contrast, the NiFe 3 supported on only CeO 2 also exhibited high activity (ethylene production rate of 0.71 µmol/g cat /s), but the ethylene selectivity (16%) was greatly decreased compared to the mixed system. Temperature programmed reduction, X-ray diffraction, and Raman spectroscopy all indicate the creation of a solid solution of the Fe and Ni doped into the CeO 2 crystal structure in the catalysts with high CeO 2 loading/bulk CeO 2 support. Here, the high ethylene selectivity in the high CeO 2 loading catalysts indicates that the Fe is preferentially creating the solid solution, with the decrease in selectivity observed in the CeO 2 -only supported catalyst likely resulting from CeO 2 interacting directly with Ni, creating Ni-CeO X interfaces that are known active sites for the unwanted side reaction of dry reforming.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Titania-Supported Single-Atom Platinum Catalyst for Water-Gas Shift Reaction

Density functional theory (DFT) and microkinetic modeling are used to examine the water-gas shift (WGS) reaction on TiO 2 (110)-supported single Pt atoms. A CO-adsorbed Pt atom supported on a TiO 2 surface exhibits a lower activity for the WGS than the Pt 2+ ion supported on a doped TiO 2 surface, although DFT predicts the CO-adsorbed Pt on an undoped TiO 2 surface to be thermodynamically more stable. Finally, trends observed in WGS activity for different active sites of TiO 2 -supported Pt catalysts can be explained in terms of CO adsorption strength and the ability to form an oxygen vacancy on the oxide support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗