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

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Stabilization of the Active Ruthenium Oxycarbonate Phase for Low-Temperature CO 2 Methanation

Interstitial carbon-doped RuO 2 catalyst with the newly reported ruthenium oxycarbonate phase is a key component for low-temperature CO 2 methanation. However, a crucial factor is the stability of interstitial carbon atoms, which can cause catalyst deactivation when removed during the reaction. In this work, the stabilization mechanism of the ruthenium oxycarbonate active phase under reaction conditions is studied by combining advanced operando spectroscopic tools with catalytic studies. Three sequential processes: carbon diffusion, metal oxide reduction, and decomposition of the oxycarbonate phase and their influence by the reaction conditions, are discussed. We present how the reaction variables and catalyst composition can promote carbon diffusion, stabilizing the oxycarbonate catalytically active phase under steady-state reaction conditions and maintaining catalyst activity and stability over long operation times. In addition, insights into the reaction mechanism and a detailed analysis of the catalyst composition that identifies an adequate balance between the two phases, i.e., ruthenium oxycarbonate and ruthenium metal, are provided to ensure an optimum catalytic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Dynamic Features of Cu-Ceria Interface under CO 2 Hydrogenation to Methanol

It is generally accepted that metal–support interaction is very important for the hydrogenation of CO 2 to methanol, but little has been revealed about the feature of interfacial active sites under real reaction conditions since there are only limited techniques that can be applied under high-pressure conditions. Here, in this work, by combining multiple in situ and operando techniques on a model Cu/ceria catalyst, we have tracked Cu and ceria sites for methanol formation. Under the reaction condition, it is found that upon reaching the reaction temperature, oxidized Cu species in the as-synthesized catalyst immediately change into metallic Cu species. Following this, it is the gradual formation of methanol, the changing rate of which coincides with the formation of a unique Ce 3+ species. The combined experimental results and density functional theory (DFT) calculations have determined that the formed Ce 3+ sites driven by the reaction conditions are bound to hydrides, adsorbed carbonate species, and interfacial active Cu sites. The Cu-ceria interaction in this complex moiety is weak and can be easily disturbed with reaction environment variations, leading to dynamic changes at the interface upon the hydrogenation of active carbonate intermediates, which are precursors for the formation of methanol. The formation of this unique Cu–Ce 3+ interface and its dynamicity lead to an increase of methanol selectivity from less than 20% to 60%. These results suggest that reactant-derived species (H – and carbonate in this work) can be essential components of the active center with the functions of manipulating the metal−oxide interaction and directing reaction pathways.

CO2 hydrogenation to methanol↗
NASA NTRS1985

A community survey of helicopter noise annoyance conducted under controlled noise exposure conditions

Reactions to low numbers of helicopter noise events (less than 50 per day) were studied in a community setting. Community residents were repeatedly interviewed about daily noise annoyance reactions on days when helicopter noise exposures were, without the residents' knowledge, controlled. The effects of maximum noise level and number of noise events on helicopter noise annoyance are consistent with the principles contained in LEQ-based noise indices. The effect of the duration of noise events is also consistent with LEQ-based indices. After removing the effect of differences in noise levels (LEQ) there is not an important difference between reactions to impulsive and nonimpulsive types of helicopters. EPNL, where corrected for number of overflights, and LEQ are approximately equally successful in representing the characteristics of noise which are related to human response. The new type of design provided estimates of the parameters in a noise reaction model which would not obtained with a similar degree of precision from conventional study designs.

Fields, J. M.↗
DOE OSTI2022

Activation of Lattice and Adatom Oxygen by Highly Stable Ceria-Supported Cu Single Atoms

Requiring catalysts to be both active yet stable over long periods of time under variable reaction conditions including high and low temperatures is a daunting challenge due to the almost mutual exclusivity of these constraints. Using CO oxidation as a probe reaction, in this work we demonstrate that thermally stable single atom copper catalysts prepared by high temperature synthesis (atom trapping) on ceria can achieve this feat by allowing modulation of the Cu charge state through facile charge transfer between active site and support. This provides the catalysts with an ability to activate either lattice or adatom oxygen atoms, accessing additional reaction channels depending on the reaction conditions. Such adaptability allows dynamic response of catalysts enabling them to remain active under variable reaction conditions. The inherent stability of the catalyst arises from the enhanced strength of the Cu-O interactions from high temperature synthesis that exist even when Cu oxidation state varies, which retards sintering and deactivation. As we show here, one can circumvent the dilemma of designing catalysts that are simultaneously active and stable by matching the redox properties of the active site and support and establishing an environmental adaptability around the active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Renewable Aromatics from Syngas

This study focuses on developing a catalytic process for the aromatization of mixed olefin (comprised of C 2 -C 6 ) over various metal doped zeolites towards the formation of large aromatics (preferably C 8 -C 16 ) compliance to the sustainable aviation fuel (SAF). Experiments were carried out using model olefin feedstocks containing either ethylene (C 2 ) or mixture of C 2 and C 3+ olefins. Both the catalyst composition and process parameters were evaluated in detail to identify their impact on the formation large aromatics. We specifically focus on the aromatization of ethylene as the model reaction and evaluated the impact of C 2+ olefins and paraffins that may present in the real feedstock. In all the reaction condition, aromatization of ethylene was used as the baseline to evaluate the effect of larger olefins or paraffins. Our results show that at this reaction condition paraffins remained either inert or show positive impact on the formation of large aromatics. While C 2 and C 3 olefins are highly reactive towards aromatization during reaction condition, large olefins are less reactive and thus, strategy was developed to oligomerize these large olefins (C 4+ ) alongside the aromatization of smaller olefins (C 2 /C 3 ).

10 SYNTHETIC FUELS↗
DOE OSTI2025

Active Sites in the Dealuminated Beta Zeolite-Supported Cobalt Catalyst for Non-Oxidative Ethane Dehydrogenation

Dispersed metal species in siliceous zeolites have been actively studied for non-oxidative dehydrogenation of ethane (NDE). Fundamental insights into the dynamics of metal species in zeolites under reaction conditions have rarely been explored. Herein, we report an atomic level understanding of the dynamics and activity of cobalt (Co) sites in dealuminated Beta zeolite (DeAl-BEA) for NDE during induction and reaction conditions with extensive characterization techniques such as diffuse reflectance UV–vis, solid state nuclear magnetic resonance and X-ray photoelectron, X-ray diffraction along with in situ Fourier transform infrared and X-ray absorption spectroscopy. For a catalyst with 0.5 mass % Co loading, tetrahedral Co 2+ mononuclear sites, di-coordinated to the zeolite framework and with two silanol groups in vicinity (i.e., (≡SiO) 2 Co(HO–Si≡) 2 ), form upon exposure to hydrogen during induction and persist through the NDE reaction. Increasing the Co loading to 3.0 mass % yielded Co sites with similar electronic and coordination structures but slightly elongated Co–O bonds. Upon cooling to room temperature, the Co sites persisted in the same coordination environment, though the disappearance of a feature in the Co K-edge near-edge region revealed changes in the active site’s electronic structure coinciding with modest shifts in bond lengths. The electronic structure and activity of (≡SiO) 2 Co(HO–Si≡) 2 sites were studied comparatively to a few other hypothetical Co 2+ coordination structures, using electronic structure calculations and microkinetic simulations. The simulations showed that NDE is controlled by β-hydride elimination following C–H bond activation and that Co-sites possessing flexibility because of neighboring silanol defects are more active. Interestingly, dinuclear Co–O–Co sites (i.e., (≡SiO)Co(HO–Si≡) 2 –O–(HO–Si≡) 2 Co(≡SiO)) were more active than the mononuclear (≡SiO) 2 Co(HO–Si≡) 2 sites because of favorable hydrogen bonding with the vicinal silanol groups. In conclusion, the present study bridges the gap between the knowledge acquired by ex-situ characterizations and the active sites under the reaction conditions in alkane dehydrogenation chemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Hydride Accessibility and Reactivity in the Configurational and Stoichiometric Space of β-Ga 2 O 3 for CO 2 Hydrogenation

Understanding how surface species evolve under reaction conditions is essential for improving catalyst design for efficient CO 2 hydrogenation. This work combines systematic DFT calculations with grand canonical sampling to investigate the stability and reactivity of Ga–H species on β-Ga 2 O 3 across a range of reaction conditions. Initial DFT studies reveal that when Ga–H species are present, they facilitate formate formation via a low-barrier pathway, largely independent of the surface termination or hydrogen site. However, grand canonical sampling shows that under a broad range of reaction conditions─especially at high oxygen chemical potentials associated with high water content─Ga–H species are thermodynamically inaccessible. Furthermore, adsorbed water molecules can block reactive sites, inhibiting CO 2 activation even when hydrides are present. These findings suggest that the lack of accessible hydride species, rather than their intrinsic reactivity, could contribute to reduced catalytic performance of β-Ga 2 O 3 under more oxidizing, high-conversion conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Low-temperature hydroformylation of ethylene by phosphorous stabilized Rh sites in a one-pot synthesized Rh-(O)-P-MFI zeolite

Zeolites containing Rh single sites stabilized by phosphorous were prepared through a one-pot synthesis method and are shown to have superior activity and selectivity for ethylene hydroformylation at low temperature (50°C). Catalytic activity is ascribed to confined Rh 2 O 3 clusters in the zeolite which evolve under reaction conditions into single Rh 3+ sites. These Rh 3+ sites are effectively stabilized in a Rh-(O)-P structure by using tetraethylphosphonium hydroxide as a template, which generates in situ phosphate species after H 2 activation. In contrast to Rh 2 O 3 , confined Rh0 clusters appear less active in propanal production and ultimately transform into Rh(I)(CO) 2 under similar reaction conditions. As a result, we show that it is possible to reduce the temperature of ethylene hydroformylation with a solid catalyst down to 50°C, with good activity and high selectivity, by controlling the electronic and morphological properties of Rh species and the reaction conditions.

Catalysis↗
NASA NTRS2004

Effects of Meteorological Conditions on Reactions to Noise Exposure

More than 80,000 residents' responses to transportation noise at different times of year provide the best, but imprecise, statistical estimates of the effects of season and meteorological conditions on community response to noise. Annoyance with noise is found to be slightly statistically significantly higher in the summer than in the winter in a seven-year study in the Netherlands. Analyses of 41 other surveys drawn from diverse countries, climates, and times of year find noise annoyance is increased by temperature, and may be increased by more sunshine, less precipitation, and reduced wind speeds. Meteorological conditions on the day of the interview or the immediately preceding days do not appear to have any more effect on reactions than do the conditions over the immediately preceding weeks or months.

Shepherd, Kevin P.↗
DOE OSTI2023

Dynamically Formed Active Sites on Liquid Boron Oxide for Selective Oxidative Dehydrogenation of Propane

Boron-based catalysts have been shown to be both active and selective for driving the oxidative dehydrogenation of propane (ODHP) without the use of precious metals. This reaction occurs at temperatures that melt the oxide catalyst which challenges our ability to identify the liquid structures of the boron oxide phase under reaction conditions, hindering the understanding of its active sites and reaction mechanism. By combining ab initio molecular dynamics simulation, in-situ Raman characterization, and microkinetic modeling, we propose that the di-coordinated boron sites (BO2) in liquid boron oxide are the active species for O2 activation under reaction conditions. The formed peroxy-like species (>B-O-O-B<) can be viewed as a moderate oxidant for ODHP. The dynamical >B-O* dangling bond originated from >B-O-O-B< site as well as the liquid B2O3 structure itself, plays a critical role in the abstraction of H atoms from propane (C3H7 radical formation). Microkinetic modeling reveals C3H7 radical formation to be the main rate controlling step (~75% degree of rate control) with the dehydration of boron hydroxyls (B-OHs) to recover the di-coordinated boron active sites controlling the remainder of the rate (~25% degree of rate control). Moreover, the activation barriers are found to strongly depend upon the surface B-OH concentration. These findings provide significant insights into the active site and reaction mechanisms on boron-based catalysts for ODHP and underlie the importance of understanding the liquid nature of the catalyst to account for the catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effect of Fe on Co-Based SiO2Al2O3 Mixed Support Catalyst for Fischer–Tropsch Synthesis in 3D-Printed SS Microchannel Microreactor

This research explores the effect of a composite support of SiO2 and Al2O3 with Fe and Co incorporated as catalysts for Fischer–Tropsch synthesis (FTS) using a 3D-printed stainless steel (SS) microchannel microreactor. Two mesoporous catalysts, FeCo/SiO2Al2O3 and Co/SiO2Al2O3, were synthesized via a one-pot (OP) method and extensively characterized using N2 physisorption, XRD, SEM, TEM, H2-TPR, TGA-DSC, FTIR, and XPS. H2-TPR results revealed that the synthesis method significantly affected the reducibility of metal oxides, thereby influencing the formation of active FTS sites. SEM-EDS and TEM further revealed a well-defined hexagonal matrix with a porous surface morphology and uniform metal ion distribution. FTS reactions, carried out in the 200–350 °C temperature range at 20 bar with a H2/CO molar ratio of 2:1, exhibited the highest activity for FeCo/SiO2Al2O3, with up to 80% CO conversion. Long-term stability was evaluated by monitoring the catalyst performance for 30 h on stream at 320 °C under identical reaction conditions. The catalyst was initially active for the methanation reaction for up to 15 h, after which the selectivity for CH4 declined. Correspondingly, the C4+ selectivity increased after 15 h of time-on-stream, indicating a shift in the product distribution toward longer-chain hydrocarbons. This trend suggests that the catalyst undergoes gradual activation or restructuring under reaction conditions, which enhances chain growth over time. The increase in C4+ products may be attributed to the stabilization of the active sites and suppression of methane or light hydrocarbon formation.

Biochemistry & Molecular Biology↗
NASA NTRS1986

The chemical shock tube as a tool for studying high-temperature chemical kinetics

Although the combustion of hydrocarbons is our primary source of energy today, the chemical reactions, or pathway, by which even the simplest hydro-carbon reacts with atmospheric oxygen to form CO2 and water may not always be known. Furthermore, even when the reaction pathway is known, the reaction rates are always under discussion. The shock tube has been an important and unique tool for building a data base of reaction rates important in the combustion of hydrocarbon fuels. The ability of a shock wave to bring the gas sample to reaction conditions rapidly and homogeneously makes shock-tube studies of reaction kinetics extremely attractive. In addition to the control and uniformity of reaction conditions achieved with shock-wave methods, shock compression can produce gas temperatures far in excess of those in conventional reactors. Argon can be heated to well over 10 000 K, and temperatures around 5000 K are easily obtained with conventional shock-tube techniques. Experiments have proven the validity of shock-wave theory; thus, reaction temperatures and pressures can be calculated from a measurement of the incident shock velocity. A description is given of the chemical shock tube and auxiliary equipment and of two examples of kinetic experiments conducted in a shock tube.

Brabbs, Theodore A.↗
DOE OSTI2026

Ag(111) Remains Significantly Reduced In Situ under Simulated Ethylene Epoxidation Conditions

Direct ethylene epoxidation is among the highest value processes in the chemical industry, yet the reaction mechanism remains debated. A central question is whether the unpromoted Ag catalyst is metallic or oxidized under reaction conditions, as this determines the active oxidant species. Using ambient pressure X-ray photoelectron spectroscopy at chemical potentials simulating industrial conditions, we find that under oxidizing environments, nucleophilic oxygen (∼80% surface coverage) and some carbonate impurities (∼20% coverage) form on Ag(111). Upon switching to an industrially relevant 5:2 ethylene-to-oxygen ratio at 433 K, nucleophilic oxygen is consumed, leaving mostly surface carbonate and bare Ag. The Ag(111) surface maintains ∼50% exposed metallic sites under these conditions. This indicates that proposed mechanisms involving a fully oxidized surface may not represent the state of the surface under relevant reaction conditions and that bare Ag sites, which are necessary to form the oxametallacycle intermediate thought to drive selective epoxidation, are available.

36 MATERIALS SCIENCE↗
NASA NTRS1981

Chemical modification of semiconductor surfaces

Results of research on the chemical modification of TiO2 powders in the gas phase and the examination of the modified powders by infrared absorption spectroscopy are comprehensively summarized. The range of information obtainable by IR spectroscopy of chemically modified semiconductors, and a definition of the optimum reaction conditions for synthesizing a monolayer of methylsilanes using vapor phase reaction conditions were considered.

Finklea, H. O.↗
DOE OSTI2020

Reaction of BCl 3 with H- and Cl-terminated Si(100) as a pathway for selective, monolayer doping through wet chemistry

The reaction of boron trichloride with the H and Cl-terminated Si(100) surfaces was investigated to understand the interaction of this molecule with the surface for designing wet-chemistry based silicon surface doping processes using a carbon- and oxygen-free precursor. The process was followed with X-ray photoelectron spectroscopy (XPS). Within the reaction conditions investigated, the reaction is highly effective on Cl-Si(100) for temperatures below 70°C, at which point both surfaces react with BCl$_3$. The XPS investigation followed the formation of a B 1s peak at 193.5 eV corresponding to (B-O)$_x$ species. Even the briefest exposure to ambient conditions lead to hydroxylation of surface borochloride species. However, the Si 2p signature at 102 eV allowed for a confirmation of the formation of a direct Si-B bond. Density functional theory was utilized to supplement the analysis and identify possible major surface species resulting from these reactions. This work provides a new pathway to obtain a functionalized silicon surface with a direct Si-B bond that can potentially be exploited as a means of selective, ultra-shallow, and supersaturated doping.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Structure Sensitivity and Catalyst Restructuring for CO2 Electro-reduction on Copper

Abstract Cu is the most promising metal catalyst for CO 2 electroreduction (CO 2 RR) to multi-carbon products, yet the structure sensitivity of the reaction and the stability versus restructuring of the catalyst surface under reaction conditions remain controversial. Here, atomic scale simulations of surface energies and reaction pathway kinetics supported by experimental evidence unveil that CO 2 RR does not take place on perfect planar Cu(111) and Cu(100) surfaces but rather on steps or kinks. These planar surfaces tend to restructure in reaction conditions to the active stepped surfaces, with the strong binding of CO on defective sites acting as a thermodynamic driving force. Notably, we identify that the square motifs adjacent to defects, not the defects themselves, as the active sites for CO 2 RR via synergistic effect. We evaluate these mechanisms against experiments of CO 2 RR on ultra-high vacuum-prepared ultraclean Cu surfaces, uncovering the crucial role of step-edge orientation in steering selectivity. Overall, our study refines the structural sensitivity of CO 2 RR on Cu at the atomic level, highlights the self-activation mechanism and elucidates the origin of in situ restructuring of Cu surfaces during the reaction.

Science & Technology - Other Topics↗
DOE OSTI2020

The production of hydrogen–deuterium exchanged cellulose fibers with exchange-resistant deuterium incorporation

Production of deuterated cellulose is important from both theoretical and practical perspectives. Here, cellulose fibers of cotton and Tencel fibers with exchange-resistant deuterium incorporation were prepared by hydrogen–deuterium exchange treatment. The effect of the micro-structure of cellulose crystallinity index as well as the reaction conditions including catalyst, reaction time, and temperature on the exchange-resistant deuterium incorporation process are reported. The ability of deuterated cellulose fibers to resist protium-exchange during H 2 O washing was also explored. The results found that higher crystallinity index is beneficial to stabilize the deuteration of cellulose fibers. Furthermore, alkaline catalysts such as sodium hydroxide or potassium carbonate and higher exchange temperature as well as longer reaction time contribute significantly to the stabilization of deuterium incorporation in the deuterated cellulose fibers. These observations revealed that the hydrogen–deuterium exchange treatment is effective to obtain exchange-resistant deuterium incorporated cellulose fibers. In addition, cotton fibers with several deuteration levels were produced and could be considered for the study of deuterium effect on cellulose properties.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Data Analytics for Catalysis Predictions: Are We Ready Yet?

Catalysis informatics has received tremendous attention in recent years as a tool to design catalysts and discover unique descriptors that capture the relationships between chemical properties and catalytic performance. One of the stop-gaps in understanding catalytic effects, which is often ignored and limits the deployment of data science tools, relates to the lack of uniform data. The catalytic cleavage of C–X (X= H, C, N, and O) bonds is relevant to many fundamental catalytic processes. In this Perspective, we performed data analytics on four groups of C–X cleavage reactions that are common in production, upcycling, or reactive separation: the C–C cleavage in cyclopropyl alcohol, the C–H cleavage in hydroacylation reactions, the C–O cleavage in β-O-4 linkages, and the C–N cleavage in amides, using experimental data collected from the literature to understand their underlying correlations. Experimental variables of high impact are identified for each reaction by dimensionality reduction methods. We highlight the urgent need for experimental data sets that include full details on the reaction conditions, such as reagent concentration, reaction temperature, or time in machine-readable forms. We discuss the potential improvement of the data of these reactions and promising approaches such as autonomous experiments to fill the gaps in unbiased experimental data. Finally, we also address the early stage consideration of separation aspects in the experimental design of efficient catalytic systems for these fundamental examples of chemical reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗