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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Capturing Surface Coverage Effects in Heterogeneous Catalysis

Adsorbate–adsorbate lateral interactions at relevant surface coverages have a significant effect on chemical kinetics, thereby influencing the activity of a heterogeneous catalyst. Coverage-dependent kinetic and thermodynamic parameters therefore must be included in studies of such complex systems to properly predict the turnover frequencies and kinetic trends. Thus, it becomes extremely important to accurately capture the strength of lateral interactions between neighboring species under realistic reaction conditions. In this Perspective, we discuss the various existing computational and experimental methods for determining adspecies coverage and configurational effects. The choice of the tools and methods employed in such studies depends on factors such as time, length scales, computational cost, the presence of solvents, and reaction conditions. The applications of each method and the respective challenges are also discussed here. As a result, we discuss the recent developments and future of the state-of-the-art for inclusion of surface coverage and configuration into a holistic picture for accurate predictions of catalytic behavior.

09 BIOMASS FUELS↗
DOE OSTI2025

Anolyte Buffering and CO Coverage Effects in the Electrochemical Reduction of CO at Cu Electrocatalysts

Electrolytic CO reduction was investigated at copper electrocatalysts in zero-gap membrane electrode assemblies as a function of buffering agents and cofeeding with CO 2 or Ar. Results show an acetate Faradaic efficiency (FE) of 90% at 300 mA cm −2 using pure CO feeds and phosphate-buffered anolyte near pH 8. When using CO feeds with more alkaline anolytes, the hydrogen evolution reaction becomes the dominant reduction reaction, independent of the buffer. Product distributions of cofeeding experiments with CO and CO 2 show that increasing CO 2 cofeeding results in increased selectivity toward ethylene (42% FE) in near-neutral KHCO 3 anolytes or ethanol (40% FE) in alkaline KOH anolytes. Evaluation of several commercial anion exchange membranes shows similar selectivity trends, suggesting product selectivity is dominated by the local pH and surface coverage of CO. Based on these results, we propose pH buffering and CO coverage behaviors that facilitate high selectivities to acetate.

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

The coverage-dependent effect on the barrier for oxygen penetration into a metal lattice

Model calculations for O/Cu(111) show that the rigid lattice penetration barrier is reduced from 8.2 to 5.3 eV as the O coverage is increased from 1/4 to 1/2 monolayer; it is expected that this large reduction will also apply to the relaxed lattice case. An increase of the distance between the first and second Cu layers, without changing the intralayer spacing, does not affect the barrier.

Bauschlicher, C. W., Jr.↗
NASA NTRS1986

Coverage dependent effects on metal surfaces - O, S, F, and Cl on Ni

The c(2 x 2) and p(2 x 2) vibrational frequencies for a rigid Ni lattice are computed for O, S, F, and Cl on Ni(100). It is found that only O/Ni(100) shows a large difference in rigid lattice vibrational frequency. A large shift in rigid lattice vibrational frequency is also found for O/Ni(111) between 0.25 and 0.5 monolayer coverages. Also associated with the change in coverage, is a change in the height above the surface R(perpendicular). This varies from a 0.11 A reduction for O/Ni(100), to an expansion of 0.06 A for F/Ni(100).

Bauschlicher, C. W., Jr.↗
DOE OSTI2026

Adsorption of CO on gold: effect of coverage and surface deformations

Recent insights into the nature of catalysts under reactive conditions have motivated investigating heterogeneously catalyzed reactions with non-rigid surfaces. As an example system to revisit, CO interactions with gold have been a longstanding system of interest due to its structure sensitivity. In this work, we investigate coverage-dependent CO adsorption trends on terraces, steps, and kinks. Calculating differential binding energy and mean absolute displacement of the atomic structures as a function of CO coverage, we propose a deformation quenching mechanism that partially determines CO saturation coverage. Extending this analysis to consider CO partial pressure, we show a phase change in CO step occupation, which we highlight as a possible explanation for previously reported temperature-programmed desorption and Fourier-transform infrared reflection-absorption spectroscopy measurements. Furthermore, this work shows how adopting a non-rigid surface model can lead to additional insights which may be applied to other heterogeneously catalyzed systems.

Kavalsky, Lance [University of Wisconsin-Madison, ↗
DOE OSTI2024

CO–induced roughening of Cu(111): formation and detection of reactive nanoclusters on metal surfaces

The formation of nanoclusters on metal surfaces in the presence of reactive environments is a phenomenon with important implications for catalysis. These nanoclusters are composed of atoms ejected from undercoordinated sites such as step edges, and their presence alters the catalytic properties of solid materials. We perform density functional theory (DFT) and kinetic Monte Carlo (KMC) simulations to investigate the formation and reactivity of copper clusters on Cu(111). Our results indicate a considerably higher reactivity of small copper nanoclusters, with up to seven atoms in size on roughened copper surfaces than on pristine Cu(111) and Cu(211). Regarding the restructuring events that give rise to nanoclusters under CO atmospheres, we determine that the ejection of Cu atoms from step edges and their migration therefrom to adjacent Cu(111) terraces are, by and large, driven by CO coverage effects. By means of KMC simulations, which account for CO–CO lateral interactions and CO–induced surface restructuring, we show that temperature programmed desorption (TPD) holds promise for the detection of highly reactive nanoclusters. Furthermore, our approach showcases how surface restructuring and surface–adsorbate bond breaking can be combined when modeling surface reactions and contributes to the development of an advanced understanding of the nature of active site under reaction conditions.

catalyst dynamic restructuring↗
DOE OSTI2026

Adsorption, charge transfer and a coverage-driven transition of alkali metals on rutile TiO 2 (110)

The interaction of alkali metals with metal oxide surfaces is central to tuning surface reactivity in heterogeneous catalysis and photocatalysis. Here we present a comprehensive DFT+U study of the adsorption of alkali metals (Li, Na, K, Rb, Cs) on the (110) surface of rutile TiO 2 . At low coverage (θ = 1/8), all alkali metals bind preferentially to bridging oxygen sites with adsorption energies in the range −4.06 to −3.33 eV, transferring nearly one full electron (0.92–0.99 |e|) to the substrate and inducing Ti 4+ → Ti 3+ reduction. The excess charge localizes preferentially at subsurface Ti sites in the form of small polarons. Diffusion barriers indicate facile motion along bridging-oxygen rows, whereas inter-row hopping is strongly hindered. Coverage effects were examined systematically for potassium: adsorption energy and charge transfer per K atom decrease monotonically with increasing θ. Strikingly, a sharp energy discontinuity occurs between θ = 4/8 and θ = 5/8 (ΔE ≈ 1 eV per atom), which we identify as a coverage-driven structural transition arising from steric packing constraints and enhanced K–K electrostatic repulsion once every (1×1) surface cell is occupied. This structural transition perfectly correlates with a dramatic drop in the work function down to an ultra-low minimum of 0.84 eV at θ=5/8, followed by a metallization- driven recovery at higher coverages. Ab initio molecular dynamics simulations confirm zigzag K arrangements at moderate coverage (θ = 1/3), while at high coverage (θ = 2/3) short-range K–K correlations emerge without long-range order. These results provide atomistic insight into the structure–activity relationships underlying alkali promotion effects on oxide-supported catalysts.

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

Materials descriptors for advanced water dissociation catalysts in bipolar membranes

The voltage penalty driving water dissociation (WD) at high current density is a major obstacle in the commercialization of bipolar membrane (BPM) technology for energy devices. Here, in this study, we show that three materials descriptors, that is, electrical conductivity, microscopic surface area and (nominal) surface-hydroxyl coverage, effectively control the kinetics of WD in BPMs. Using these descriptors and optimizing mass loading, we design new earth-abundant WD catalysts based on nanoparticle SnO 2 synthesized at low temperature with high conductivity and hydroxyl coverage. These catalysts exhibit exceptional performance in a BPM electrolyser with low WD overvoltage (η wd ) of 100 ± 20 mV at 1.0 A cm -2 . The new catalyst works equivalently well with hydrocarbon proton-exchange layers as it does with fluorocarbon-based Nafion, thus providing pathways to commercializing advanced BPMs for a broad array of electrolysis, fuel-cell and electrodialys is applications.

Sasmal, Sayantan↗
DOE OSTI2026

Identification of Carbonyl Species on Palladium Supported on Ceria in Complex Microenvironments

Herein, we present a systematic comparison between Pd carbonyl (Pd-CO) species, specifically over Pd/CeO 2 based catalysts, observed during isothermal adsorption and in several prototypical catalytic reactions to identify and understand CO adsorption on palladium-ceria based catalysts. Pd-CO is observed via DRIFTS to probe the gas-solid conditions, while ATR-IR is used to probe the affinity of Pd-CO under more complex solvated gas-solid-liquid conditions to discern the influence of the microenvironments for carbonyl adsorption. Here, we explore the presence of Pd-CO under several reactive environments, including CO adsorption, CO 2 + H 2 , CO + H 2 , CH 4 + CO 2 and CO under gas-solid-liquid media, highlighting reactions with notable Pd-CO formation. The differences between palladium carbonyls and carbonate species show that carbonyl species are much more affected via a shifting of the peak position than carbonates, which remain static irrespective of the immediate chemical environment. By following the rate of CO accumulation via K-M mode DRIFTS, we observe migration from linear, 2095 cm -1 , to bridge site, 1978 cm -1 , as a function of time under a static CO atmosphere. With the use of DFT, we discerned changes in Pd-carbonyl stretches due to both coverage effects of CO under simulated reaction conditions and temperature effects. Regardless of whether CO is formed as an intermediate or a reactant, the competitive adsorption of *H and *CO affects the binding strength of *CO at all temperatures, with low temperature favoring atop binding and high temperature favoring the more stable FCC Pd-CO site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A Lens into the Cu Nanograin by In Situ Vibrational Spectroscopy

Cu-based catalysts are uniquely capable of C-C coupling during electrochemical CO 2 reduction (CO 2 R), yet further mechanistic understanding remains hampered by the lack of spectroscopically resolved descriptors that demonstrate how surface adsorbates emerge and evolve within their catalytic environment. Here, in this study, we correlate in situ surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRAS) to resolve the potential-dependent dynamics during CO 2 R on Cu nanograin catalysts. By building on previous benchmarking of low overpotential performance and nanograin structural evolution, we offer a diagnostic framework linking vibrational signatures to catalytic function, unveiling which species appear, persist, and turnover as the electrified surface and interfacial environment evolve under bias. The onset of linear CO is marked below -0.45 V, coincident with persistent adsorbed *OH/*O domains beyond the CO 2 R onset. In this context, Cu nanograins serve as a platform to dissect contributions of adsorbate coverage. By carefully dissecting the potential dependence of emergent twin-defect/step CO stretch bands (P1-P2), alongside the prototypical terrace-site CO stretch band (P3), we provide important context for interpreting coupled spectroscopic trends driven by coverage effects and resolve this for the evidently complex nanograin morphology. Together, these observations highlight the intertwined roles of surface stabilization and interfacial flux in steering multicarbon product formation. By directly linking vibrational signatures to catalytic behavior, this work aims to bridge the gap between observation and control and help guide toward a predictive framework of fine-tuned selectivity for CO 2 R.

Fonseca Guzman, Maria V. [University of California↗
DOE OSTI2026

X-ARAPUCA Photon Detectors in SBND

The Short-Baseline Near Detector (SBND) is a liquid argon time projection chamber (LArTPC) for detecting neutrinos from Fermilab's Booster Neutrino Beam. Located 110 m downstream of the beam target, SBND collects both ionization electrons and scintillation photons from particle interactions within the detector volume. The photon detection system (PDS) consists of both PMTs and X-ARAPUCAs, a novel technology featuring large area cost-effective coverage with single photo-electron resolution at cryogenic temperatures. SBND utilizes two types of X-ARAPUCAs: one sensitive to vacuum ultra-violet (VUV) scintillation light produced and one sensitive to visible light for the light reflected off TPB-coated reflective foils. SBND is the only experiment currently testing the X-ARAPUCA technology in a neutrino beam over a period of several years, and will provide critical information for deployment in future detectors like DUNE. This poster will cover the calibration and early performance of X-ARAPUCAs in SBND.

Dalager, Olivia [Fermilab]↗
NASA NTRS1979

Power Extension Package (PEP) system definition extension, orbital service module systems analysis study. Volume 7: PEP logistics and training plan requirements

Recommendations for logistics activities and logistics planning are presented based on the assumption that a system prime contractor will perform logistics functions to support all program hardware and will implement a logistics system to include the planning and provision of products and services to assure cost effective coverage of the following: maintainability; maintenance; spares and supply support; fuels; pressurants and fluids; operations and maintenance documentation training; preservation, packaging and packing; transportation and handling; storage; and logistics management information reporting. The training courses, manpower, materials, and training aids required will be identified and implemented in a training program.

Source record↗
NASA NTRS1992

The hard x ray luminosity function and evolution of AGN

A large number of active galactic nuclei and quasars detected by the HEAO A1 x-ray survey and recently identified using results from the HEAO A3 experiments are described and preliminary results are presented. The sample shows some incompleteness and is not completely identified, so these effects are taken out in the analysis by correcting the effective coverage of the survey. Preliminary analysis indicates that significant evolution can be detected in this data and that the evolution rate appears stronger than that inferred from a sample selected at lower energies.

Marshall, Herman L.↗
NASA NTRS1991

Evolution of the X-ray luminosity function of AGN

The HEAO A1 X-ray survey has detected a large number of active galactic nuclei and quasars, as recently identified using results from the HEAO A3 experiment. The sample shows some incompleteness and is not completely identified, so these effects are taken out in the analysis by correcting the effective coverage of the survey. Preliminary analysis indicates that significant evolution can be detected in these data and that the evolution rate appears stronger than that inferred from a sample selected at lower energies.

Marshall, Herman L.↗
NASA NTRS1984

Vortex generating flow passage design for increased film-cooling effectiveness and surface coverage

The fluid mechanics of the basic discrete hole film cooling process is described as an inclined jet in crossflow and a cusp shaped coolant flow channel contour that increases the efficiency of the film cooling process is hypothesized. The design concept requires the channel to generate a counter rotating vortex pair secondary flow within the jet stream by virture of flow passage geometry. The interaction of the vortex structures generated by both geometry and crossflow was examined in terms of film cooling effectiveness and surface coverage. Comparative data obtained with this vortex generating coolant passage showed up to factors of four increases in both effectiveness and surface coverage over that obtained with a standard round cross section flow passage. A streakline flow visualization technique was used to support the concept of the counter rotating vortex pair generating capability of the flow passage design.

Papell, S. S.↗
NASA NTRS1984

Vortex-generating coolant-flow-passage design for increased film-cooling effectiveness and surface coverage

The thermal film-cooling footprints observed by infrared imagery for three coolant-passage configurations embedded in adiabatic-test plates are discussed. The configurations included a standard round-hole cross section and two orientations of a vortex-generating flow passage. Both orientations showed up to factors of four increases in both film-cooling effectiveness and surface coverage over that obtained with the round coolant passage. The crossflow data covered a range of tunnel velocities from 15.5 to 45 m/sec with blowing rates from 0.20 to 2.05. A photographic streakline flow visualization technique supported the concept of the counterrotating apability of the flow passage design and gave visual credence to its role in inhibiting flow separation.

Papell, S. S.↗
NASA NTRS2023

Impact of COVID-19-related Air Traffic Reductions on the Coverage and Radiative Effects of Linear Persistent Contrails over Conterminous United States and Surrounding Oceanic Routes

The radiative effects of the large-scale air traffic slowdown during Apr and May 2020 due to the international response to the COVID-19 pandemic are estimated by comparing the coverage (CC), optical properties, and radiative forcing of persistent linear contrails over the conterminous United States and two surrounding oceanic air corridors during the slowdown period and a similar baseline period during 2018 and 2019 when air traffic was unrestricted. The detected CC during the slowdown period decreased by an area-averaged mean of 41% for the three analysis boxes. The retrieved contrail optical properties were mostly similar for both periods. Total shortwave contrail radiative forcings during the slowdown were 34 and 42% smaller for Terra and Aqua, respectively. The corresponding differences for longwave contrail radiative forcing were 33% for Terra and 40% for Aqua. To account for the impact of any changes in the atmospheric environment between baseline and slowdown periods on detected CC amounts, the contrail formation potential (CFP) was computed from reanalysis data. In addition, a filtered CFP (fCFP) was also developed to account for factors that may affect contrail formation and visibility of persistent contrails in satellite imagery. The CFP and fCFP were combined with air traffic density data to create empirical models that estimated CC during the baseline and slowdown periods and were compared to the detected CC. The models confirm that decreases in CC and radiative forcing during the slowdown period were mostly due to the reduction in air traffic, and partly due to environmental changes.

contrails↗