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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 865 records · Page 48
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

X-ray quantification of oxygen groups on diamond surfaces for quantum applications

Abstract Identifying the surface chemistry of diamond materials is increasingly important for device applications, especially quantum sensors. Oxygen-related termination species are widely used because they are naturally abundant, chemically stable, and compatible with stable nitrogen vacancy centres near the diamond surface. Diamond surfaces host a mixture of oxygen-related species, and the precise chemistry and relative coverage of different species can lead to dramatically different electronic properties, with direct consequences for near-surface quantum sensors. However, it is challenging to unambiguously identify the different groups or quantify the relative surface coverage. Here we show that a combination of x-ray absorption and photoelectron spectroscopies can be used to quantitatively identify the coverage of carbonyl functional groups on the { 100 } diamond surface. Using this method we reveal an unexpectedly high fraction of carbonyl groups ( > 9%) on a wide range of sample surfaces. Furthermore, through a combination of ab initio calculations and spectroscopic studies of engineered surfaces, we reveal unexpected complexities in the x-ray spectroscopy of oxygen terminated diamond surfaces. Of particular note, we find the binding energies of carbonyl-related groups on diamond differs significantly from other organic systems, likely resulting in previous misestimation of carbonyl fractions on diamond surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The role of the spatial heterogeneity and correlation length of surface wettability on two-phase flow in a CO 2 -water-rock system

This study characterized and modeled heterogeneous surface wettability in sandstone and investigated the role of spatial heterogeneity and correlation length of surface wettability on relative permeability in a supercritical CO 2 (scCO 2 )-brine-rock system. Understanding the role of wettability heterogeneity on relative permeability is essential to geological CO 2 sequestration, oil and gas recovery, and contaminated groundwater remediation. Although numerous studies have attempted to understand the influences of surface wettability, capillary number (Ca), and viscosity ratio, the role of the spatial variation and correlation length of surface wettability on two-phase flow in three-dimensional (3D) porous media has not been unraveled due to the challenges in the measurement and representation of realistic rock surface wettability. In this work, we conducted in-situ measurements of surface contact angle (CA) in a Bentheimer sandstone after CO 2 flooding using micro-computed tomography (micro-CT), and found that the pore-scale CA distribution on rock surfaces followed a log-normal distribution associated with a spatial correlation length. Based on the statistical information from CT scanning, a Gaussian random field was used to model CA distributions that had desired standard deviations and spatial correlation lengths, which were then adjusted within a certain range of values for sensitivity analyses to study their combined effects on the two-phase flow in the porous medium using the lattice Boltzmann (LB) method. The LB two-phase flow simulation was accelerated using hybrid, multicore parallel computing to overcome the challenges in simulating multiphase flow in a large 3D domain having 800 × 800 × 600 nodes. The simulation results showed that the surface wettability heterogeneity (i.e., standard deviation of CA) had a lesser effect on the relative permeability of the wetting fluid (water) but a more significant impact on the relative permeability of the non-wetting fluid (scCO 2 ). The Corey model was used to fit the LB-simulated relative permeability curves of water and scCO 2 and showed that the variations in the relative permeability curves for both water and scCO 2 increased as the standard deviation and spatial correlation length of CA increased. This study illustrated that the assumption of homogeneous surface wettability may cause errors in multiphase flow simulations. Furthermore, the impacts of both the standard deviation and spatial correlation length of CAs should be accounted for. This is the first study that explored the spatial correlation lengths associated with CA distributions on sandstone surfaces and comprehensively investigated the roles of both spatial variation and correlation length of CA on two-phase flow properties in 3D porous media. The optimized LB multiphase flow model was proved a powerful tool to study the interplays and combined effects of these statistical parameters, which had critical applications in numerous natural and engineering processes that involved multiphase flow in porous media.

58 GEOSCIENCES↗
DOE OSTI2020

Migration energy barriers and diffusion anisotropy of point defects on tungsten surfaces

We report tungsten is one of the most promising candidates for plasma-facing materials in future fusion devices, owing to its high performance under extreme irradiation conditions. However, irradiation-induced surface morphology varies significantly, depending on the irradiation type, fluence, and flux. Therefore, it is critical to examine the dynamics of point defects on tungsten (W) surfaces to understand how irradiation affects surface morphology. In this study, we employ the Self-Evolving Atomistic Kinetic Monte Carlo (SEAKMC) method to search for potential migration paths of point defects on W (1 0 0), (1 1 0) and (1 1 1) surfaces. The first-principles calculations are then used to accurately determine the migration energy barriers. The obtained paths and barriers are incorporated into a kinetic Monte Carlo (KMC) model to determine trajectories and diffusivities, which are described by diffusion tensors to demonstrate their anisotropic features. Multiple diffusion mechanisms have been identified on different surfaces, with various anisotropy factors. Particularly, point defects on the W (1 1 0) surface have the highest diffusivities, with anisotropy factors independent of temperatures. In comparison, the anisotropy of the W (1 0 0) surface decreases as temperature increases, while the W (1 1 1) surface is isotropic for point defects. This study provides insights into defect transport properties on different surfaces, which are essential for understanding the early stages of irradiation-induced microstructural evolutions and surface morphology of tungsten.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Water-induced surface ordering facilitating the microcutting of ductile metals

Metal cutting is a crucial process in modern manufacturing. Enhancing the machinability of metals can significantly improve their production efficiency and surface integrity. Coating surface-active media (SAM) on the free surface of the metals before cutting is an easy method to improve machinability, which usually pertains to the category of the renowned Rehbinder effect. However, the existing SAM is usually hazardous and complex materials. Besides, the effect of SAM on the local structure of the metal surface remains unclear. In this study, water is employed as a simple yet often overlooked SAM in the microcutting of copper. Using water as SAM also allows the employment of X-ray absorption fine structure spectroscopy (XAFS) to study the local structure of copper with and without water coating. Results show that water coating on the free surface of copper can significantly reduce the cutting force and chip thickness, and improve the surface finish. Interestingly, removing the water coating enables the recovery of the cutting force, demonstrating a reversible effect. Based on the XAFS results and molecular dynamics simulation, a water-induced surface ordering mechanism is proposed to explain the findings from the microcutting experiments. This mechanism suggests that water molecules can induce surface ordering in copper, resulting in reduced surface energy and fracture toughness of copper, thus enhancing machinability. In conclusion, this work provides valuable insights into the comprehension of the Rehbinder effect and shows that picometer-scale modifications of the surface atom arrangement can considerably alter the deformation mode of metals, paving the way for the development of new manufacturing processes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

First-principles study of the surface properties of uranium carbides

Uranium carbides have attracted renewed interest as advanced nuclear fuels for Generation IV reactors. As an important property required for gas bubble modeling in nuclear fuels, the surface energy of uranium carbides is scarce in literature. In this work, we study the surface properties of uranium carbides by first-principles density functional theory calculations. Surface orientations with maximum Miller index up to 3, 2 and 2 are investigated for UC, U 2 C 3 and α-UC 2 , respectively. By studying the effects of surface termination and chemical potential on surface energy, we identify the factors that determines the surface stability. From the calculated surface energies, the surface properties of uranium carbide single crystals are obtained from Wulff construction, including equilibrium morphology, dominant surface orientation and area weighted surface energy.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ab-initio predictions of phase stability, electronic structure, and optical properties of (0001)-MAX surfaces in M 2 AC (M = Cr, Zr, Hf; A = Al, Ga)

In this work, we report MAX phases' surface properties, which are essential for thin-film technology due to their excellent resistance to high-temperature oxidation, corrosion, and wear. The surface stability, electronic, and optical properties of 0001-surfaces in M 2 AC (M = Zr, Hf, Cr; A = Al, Ga) are investigated and compared with their bulk counterparts. The interplay between chemical bonding and charge distribution is discussed from electronic structure, including the Fermi surfaces. Four possible (0001)-terminated surfaces are considered by breaking M - C and M-A bonds in which cleavage energy of M - C is higher than M-A. The Cr–Al bond in Cr 2 AlC is stronger than other M-A bonds. The charge density of valance A-p electrons redistributes in the surface area, distinct from that of the bulk. The A- and M(C)-terminated (0001)-surfaces are the most stable and energetically favorable terminations due to lower surface energies. The optical properties of the most stable (0001)-surfaces were also investigated to understand the dielectric and photoconductive behavior in the (0001)-terminated surfaces of M 2 AC.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Surface Finishing and Coating Parameters Impact on Additively Manufactured Binder-Jetted Steel–Bronze Composites

In this paper, electroless nickel plating is explored for the protection of binder-jetting-based additively manufactured (AM) composite materials. Electroless nickel plating was attempted on binder-jetted composites composed of stainless steel and bronze, resulting in differences in the physicochemical properties. We investigated the impact of surface finishing, plating solution chemistry, and plating parameters to attain a wide range of surface morphologies and roughness levels. We employed the Keyence microscope to quantitatively evaluate dramatically different surface properties before and after the coating of AM composites. Scanning electron microscopy revealed a wide range of microstructural properties in relation to each combination of surface finishing and coating parameters. We studied chempolishing, plasma cleaning, and organic cleaning as the surface preparation methods prior to coating. We found that surface preparation dictated the surface roughness. Taguchi statistical analysis was performed to investigate the relative strength of experimental factors and interconnectedness among process parameters to attain optimum coating qualities. The quantitative impacts of phosphorous level, temperature, surface preparation, and time factor on the roughness of the nickel-plated surface were 17.95%, 8.2%, 50.02%, and 13.21%, respectively. On the other hand, the quantitative impacts of phosphorous level, temperature, surface preparation, and time factor on the thickness of nickel plating were 35.12%, 41.40%, 3.87%, and 18.24%, respectively. The optimum combination of the factors’ level projected the lowest roughness of Ra at 7.76 µm. The optimum combination of the factors’ level projected the maximum achievable thickness of ~149 µm. This paper provides insights into coating process for overcoming the sensitivity of AM composites in hazardous application spaces via robust coating.

36 MATERIALS SCIENCE↗
NASA NTRS2014

Impact of Land Surface Initialization Approach on Subseasonal Forecast Skill: a Regional Analysis in the Southern Hemisphere

The authors use a sophisticated coupled land-atmosphere modeling system for a Southern Hemisphere subdomain centered over southeastern Australia to evaluate differences in simulation skill from two different land surface initialization approaches. The first approach uses equilibrated land surface states obtained from offline simulations of the land surface model, and the second uses land surface states obtained from reanalyses. The authors find that land surface initialization using prior offline simulations contribute to relative gains in subseasonal forecast skill. In particular, relative gains in forecast skill for temperature of 10%-20% within the first 30 days of the forecast can be attributed to the land surface initialization method using offline states. For precipitation there is no distinct preference for the land surface initialization method, with limited gains in forecast skill irrespective of the lead time. The authors evaluated the asymmetry between maximum and minimum temperatures and found that maximum temperatures had the largest gains in relative forecast skill, exceeding 20% in some regions. These results were statistically significant at the 98% confidence level at up to 60 days into the forecast period. For minimum temperature, using reanalyses to initialize the land surface contributed to relative gains in forecast skill, reaching 40% in parts of the domain that were statistically significant at the 98% confidence level. The contrasting impact of the land surface initialization method between maximum and minimum temperature was associated with different soil moisture coupling mechanisms. Therefore, land surface initialization from prior offline simulations does improve predictability for temperature, particularly maximum temperature, but with less obvious improvements for precipitation and minimum temperature over southeastern Australia.

Precipitation↗
NASA NTRS2018

Tactical Surface Metering Procedures for Charlotte Douglas International Airport

NASA has been collaborating with the Federal Aviation Administration (FAA) and aviation industry partners to develop and demonstrate new concepts and technologies for the Integrated Arrival, Departure, and Surface (IADS) traffic management capabilities under the Airspace Technology Demonstration 2 (ATD-2) project. The primary goal of the ATD-2 project is to improve the predictability and the operational efficiency of the air traffic system in metroplex environments while maintaining or improving throughput by enhancing and integrating arrival, departure and surface prediction, scheduling, and management systems. In the Phase 1 Baseline IADS Demonstration, the tactical surface scheduling capability and the user interfaces for ramp controllers and ramp traffic managers were implemented for ramp operations. The purpose of the tactical surface scheduling capability is to provide the airline ramp controller with aircraft pushback advisories that prevent surface congestion and to respond to surface and airspace constraints that become known over relatively short time horizons. For this purpose, the tactical surface metering tool first estimates the capacity of current and near-future runway resources from flight schedule and surveillance data. With demand forecasts and predicted taxi trajectories, this tool computes an efficient runway schedule of aircraft in the planning horizon based on their readiness, Earliest Off-Block Times (EOBTs), and a ration by schedule (RBS) rule. Details on the implementation of the Tactical Surface Metering tool will be provided in the full paper. Both pushback and recommended hold times advisories provided by this surface metering tool are shown on the user interfaces for the ramp controller and the ramp traffic manager, called Ramp Traffic Console (RTC) and Ramp Manager Traffic Console (RMTC), respectively. There is excess queue time in the system due to demand capacity imbalance, this time can be taken as a hold on the runway queue or at the gate and was referred to as the Metering Value. This metering value can be adjusted by the Ramp Manager in collaboration with Air Traffic Controller-Tower Traffic Management Coordinator (TMC). They selected a set of metering values as default values for the tool during human-in-the-loop simulation. As the metering value increases, there is a decrease in the gate hold and increase in the queue time at the runway. Procedures and Information needs related to managing the surface metering procedures were researched in the simulated environment. These procedures will be compared to the procedures adopted at Charlotte Douglas International Airport when the tools were deployed and adopted in November 2017 for one departure push bank per day. Feedback regarding initial issues, information needs such as the need to see EOBTs on the flight data tags and how they compare to scheduled times will also be discussed in the full paper. Initial results will be provided regarding the choice of the metering value and how it was adjusted on a daily basis and what procedures evolved will also be presented in the paper.

surface metering↗
NASA NTRS2018

Development of a Detailed Surface Chemistry Framework in DSMC

A generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the Direct Simulation Monte Carlo (DSMC) solver SPARTA (Stochastic PArallel Rarefied-gas Time-accurate Analyzer). The various mechanisms include adsorption, desorption, Eley-Rideal (ER), and several types of Langmuir-Hinshelwood (LH) mechanisms. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., adsorption, ER) and pure-surface (e.g., desorption) reaction mechanisms are incorporated, and the framework also includes catalytic or surface altering mechanisms involving the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and a similar convention is adopted in the current work. Expressions for the microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are required for DSMC are derived from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are specified according to the reaction type and input parameters. This framework also presents physically consistent procedures to accurately compute the reaction probabilities and frequencies in the case of multiple reactions. The result is a modeling tool with a wide variety of surface reactions characterized via user-specified reaction rate constants, surface properties and parameters.

Surface Chemistry↗
NASA NTRSDate not supplied

Global Surface Skin Temperature Monitoring from Satellites

Surface skin temperature has been retrieved from IASI measurements. Monthly and spatially gridded surface skin temperature is produced to show some phenomena of its natural variability, which is also reflected in the surface emissivity and/or soil moisture derived from the same time series of measurements. The anomalies of surface skin temperature are used to estimate its trend. Error estimation and/or evaluation has been performed and discussed to understand the uncertainty in the trends. The trend of IASI global surface skin temperature is compared with that of NASA GISS global surface air temperature. Despite the physical differences between surface skin and air temperatures, agreement is shown between these two datasets indicating consistency and global surface warming during the past 15 years. The trend of IASI global surface skin temperature reports a positive increase has evolved during 2007–2022. This warming trend is more pronounced in the northern hemisphere. Retrieving, analyzing, and monitoring surface parameters from such advanced hyperspectral infrared sounders will continue.

global warming↗
NASA NTRSDate not supplied

NASA Lunar Surface Operations & Power Grid

The National Aeronautics and Space Administration (NASA) Artemis Program is developing, testing, and demonstrating new capabilities and technologies required to support a sustainable human presence on the lunar surface and a longer-term vision of sending astronauts to Mars. Artemis lunar surface operations will begin with robotically exploring the lunar south polar regions for locations suitable for harvesting lunar surface resources. Over time activities on the lunar surface will expand beyond robotic operations to human lunar surface operations with the delivery of a lunar habitat and in-situ resource utilization (ISRU) assets increasing the need for highly reliable and available electrical power. As operations move beyond the Artemis technology demonstrations and exploration activities towards full commercial lunar surface activities, the ability to expand the original envisioned Artemis power system and repurpose power system components to support commercial activities will be crucial. One technology that will be necessary to support commercial lunar operations is a power grid. A lunar surface power grid would offer the ability to integrate various power sources to maximize power availability, including fission surface power (nuclear), solar arrays, batteries, and regenerative fuel cells. Newly designed terrestrial microgrids are flexible and can be designed to allow for islanded operation, where power is utilized near the loads to minimize power distribution losses or in a power sharing mode where power is transmitted longer distances. This capability is crucial during failures where overall power availability is reduced, and load demand exceeds generation/storage capability. These terrestrial microgrids will also allow for the power system to grow and evolve over time, meeting the need to expand beyond initial lunar surface activities. This presentation will discuss the NASA Artemis plans, potential power system architectures, and power distribution options that will enable growth from initial technology demonstrations towards a lunar economy with a lunar surface power grid that offers many of the advantages of terrestrial microgrids.

Microgrids↗
NASA NTRSDate not supplied

LANDO: Developing Autonomous Payload Offloading Capabilities for Lunar Surface Operations

Introduction: The Lightweight Surface Manipulation System (LSMS) AutoNomy capabilities Development for surface Operations and construction (LANDO) project is an Early Career Initiative selected for funding by NASA Space Technology Mission Directorate. LANDO is developing a general-purpose autonomy framework applicable to serial and tension-actuated manipulation agents, that will be validated using an existing prototype of the LSMS-L35 (35-kg wrist lift capacity on the lunar surface [Fig. 1], sized for a Commercial Lunar Pay-load Services (CLPS) mission). The autonomous LSMS-L35 will be used to demonstrate autonomous payload handling capabilities for Lunar and other planetary surfaces, directly addressing STMD capability gaps in autonomous excavation and construction operations, advanced robotics and spacecraft autonomy technologies, and technologies supporting emerging space industries including the In-Space Servicing, Assembly and Manufacturing national strategy. LSMS: The LSMS is a tension actuated robotic agent that is scalable (reach and lifting capacity in different gravity environments), versatile (types of surface operations), and reusable. Compared to serial arms, the LSMS provides significantly higher structural efficiency and mechanical advantage, enabling a greater payload lift capacity at a lower system mass. The LSMS is envisioned to be a crucial part of the excavation and construction portfolio, capable of supporting a variety of activities on the lunar surface. Autonomous payload handling is one of the first activities the LSMS can support that develops capabilities that are extensible to other surface operations. Payload handling is required to: remove payloads from a lander; place payloads on mobile agents for transport from a lander to construction site/assembly point; emplace payloads in their operational configuration, and aggregate components to create an asset. As an example of this critical gap, manifested CLPS missions do not currently have a ubiquitous payload offloading capability; payloads (excluding rovers) are designed to remain on the lander. Why Autonomy? Autonomous robotic systems capable of carrying out excavation and construction operations are a fundamental and critical capability required for realizing the NASA Artemis program vision to “emplace and build the infrastructure, systems, and robotic missions that can enable a sustained lunar surface presence.” While teleoperation is still feasible for lunar surface operations, increased latency at Mars will require validated supervised autonomous technologies capable of operating with minimal human involvement (human-on-the-loop) unless an unexpected event occurs requiring human intervention. Autonomy reduces operator burden, allows operations to continue during uncrewed periods, in-creases the safety of operations by automatically detecting and handling faults, and allows operating in high latency environments. Development Activities: LANDO is extending critical autonomous operations to the manipulation domain and creating an integrated system, based on reusable software modules, that is capable of planning and executing payload handling and autonomous surface operations without requiring hu-man intervention beyond a supervisory role. The priority features under development are 1) autonomously offload payloads from a tilted lander deck without buckling the LSMS; 2) sensing whether a payload is safe to lift and handle; and 3) integrate with Astrobotic’s CLPS lander. The poster presentation will highlight current development activities over the past year on LSMS-L35 prototype hard-ware design, and autonomy software.

in-space assembly↗
DOE OSTI2023

Daytime convective development over land: the role of surface forcing

Water availability at the Earth surface determines the portioning of the surface heat flux into its sensible and latent components, that is, the surface heat flux Bowen ratio. The two components affect differently the surface buoyancy flux and thus the development and growth of the convective boundary layer. As a result, the Bowen ratio has a strong impact on the daytime dry and moist convection development over land. Here, we use two canonical modeling test cases, one for the shallow convection and one for the shallow-to-deep convection transition, to document the impact of the surface Bowen ratio on daytime convection development. A simple approach is used where results from simulations featuring the original setup are contrasted with simulations where surface sensible heat flux takes on values of the latent heat flux and vice versa. Such a change illustrates the key impact of the surface water availability without changing the total surface heat flux. Because of the larger surface buoyancy flux, simulations with the reversed surface heat fluxes feature faster deepening of the convective boundary layer and wider clouds once moist convection develops. Mean cloud base width of cumulus clouds increases with the boundary layer depth. For shallow-to-deep convection transition, comparison of simulations with the observed large-scale flow that feature substantial lower-tropospheric shear with simulations with no mean horizontal flow suggests that the organization of convective circulations within the boundary layer strongly affects initial size and organization of shallow convection, as well as the subsequent width increase once convection deepens and eventually transitions to deep precipitating convection. A simple explanation is provided of why deeper well-mixed convective subcloud layer results in wider clouds. The key is the larger width of boundary layer coherent updraft structures when the mixed layer is deeper.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Pd3Ag(111) as a Model System for Hydrogen Separation Membranes: Combined Effects of CO Adsorption and Surface Termination on the Activation of Molecular Hydrogen

Abstract The co-adsorption of hydrogen and carbon monoxide on Pd 3 Ag(111) alloy surfaces has been studied as a model system for Pd-Ag alloys in membrane and catalysis applications using periodic density functional theory calculations (PW91-GGA). We explored the effects of Pd–Ag surface composition, since segregation of silver towards and away from the surface has been suggested to explain the experimentally observed changes in H 2 activation, CO inhibition and reactivity. We found that CO pre-adsorbed on the surface weakens the adsorption of H on Pd 3 Ag(111) alloy surfaces irrespective of whether the surface termination corresponds to the bulk Pd 3 Ag composition, or is purely Pd-terminated. A higher coverage of H with CO present is obtained for the Pd-terminated surface; this surface also exhibits a larger range of chemical potentials for co-adsorbed hydrogen and CO. The barrier for H 2 activation increases with increasing CO coverage, but the surface composition has the largest impact on H 2 activation at intermediate CO coverage. The results imply that Pd-based membranes with typically ~ 23 wt% Ag are less prone to CO poisoning if the surface becomes Pd-terminated.

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

Ghost states and surface structures of the charge density wave kagome metal ScV 6 Sn 6

In this work, we investigate the high-temperature phase of the kagome metal ScV 6 Sn 6 using scanning tunneling microscopy/spectroscopy (STM/S) and density functional theory calculations. STM topographic images of the cleaved sample reveal two distinct surface terminations: flat islands with Sn termination and trenches terminated by kagome layers with Sn as the outermost atomic layer. STS measurements on the Sn-terminated and kagome-terminated surfaces show significant differences, in particular the presence of large density of states near the Fermi level in the former case. Our first-principles calculations reveal that the charge density on the kagome-terminated surface gives rise to “ghost states” which show intensity away from surface atoms, arising due to hybridization of orbitals above the surface. These states can obscure the intrinsic properties of the surface, potentially leading to misattribution of the surface termination. This underscores the need for careful interpretation in STM studies, especially when discerning surface states of localized states. Understanding the surface structure of this versatile quantum material provides essential information for interpreting surface-sensitive experiments, tailoring material properties, engineering interfaces, and controlling stability and reactivity. This knowledge paves the way for further exploration and potential applications of kagome lattice materials in various fields, including quantum computing, topological physics, and advanced electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Measurement and analysis of the Doppler broadened energy spectra of gamma radiation originating from the annihilation of positrons incident on clean and adsorbate-covered surfaces

We present measurements and theoretical modeling demonstrating the capability of coincidence Doppler broadened (CDB) annihilation gamma spectroscopy to provide element-specific information from the topmost atomic layer of surfaces. Our measurements show that the energy spectra of Doppler-shifted annihilation gamma photons emitted following the annihilation of positrons from the topmost atomic layers of clean and adsorbate covered surfaces of gold (Au), silver (Ag) and copper (Cu) differ significantly. The shape of the Doppler-broadened gamma spectrum, as analyzed using ratio curves, indicates that the elemental composition of the surface can still be identified despite contributions from positronium annihilation and a significant reduction in core electron annihilation. We estimate the chemical composition of the various probed surfaces by modeling the ratios of the measured Doppler spectra with respect to the Doppler spectra from a clean Cu surface using a linear combination of calculated ratio curves. The fitting of the experimental ratio curves was used to obtain an estimate of the elemental composition of Cu surfaces with sulfur segregation, oxygen adsorption, a thin film of Selenium (Se), and a single layer of graphene (SLG). A similar analysis was performed on the Ag surface with environmental adsorbates, the same surface after argon ion sputtering, as well as a sputter cleaned Au surface. The surface compositions obtained from the analysis of the CDB data were compared to the compositions obtained using positron annihilation induced Auger electron spectroscopy (PAES). Our results show that CDB can detect, identify, and quantify, sub-monolayer adsorbates and a single atomic layer deposited on metal substrates.

Lotfimarangloo, Sima [Univ. of Texas, Arlington, T↗
DOE OSTI2024

Site heterogeneity and broad surface-binding isotherms in modern catalysis: Building intuition beyond the Sabatier principle

Learning the science of heterogeneous catalysis and electrocatalysis always starts with the simple case of a flat, uniform surface with an ideal adsorbate. It has of course been recognized for a century that real catalysts are more complicated. For the increasingly complex catalysts of the 21st century, this Perspective argues that surface heterogeneity and non-ideal binding isotherms are central features, and their implications need to be incorporated in current thinking. A variety of systems are described herein where catalyst complexity leads to broad, non-Langmuirian surface isotherms for the binding of hydrogen atoms – and this occurs even for ideal, flat Pt(111) surfaces. Modern catalysis employs nanoscale materials whose surfaces have substantial step, edge, corner, impurity, and other defect sites, and they increasingly have both metallic and non-metallic elements M n X m , including metal oxides, chalcogenides, pnictides, carbides, doped carbons, etc. The surfaces of such catalysts are often not crystal facets of the bulk phase underneath, and they typically have a variety of potential active sites. Catalytic surfaces in operando are often non-stoichiometric, amorphous, dynamic, and impure, and often vary from one part of the surface to another. Understanding of the issues that arise at such nanoscale, multi-element catalysts is just beginning to emerge. Yet these catalysts are widely discussed using Brønsted/Bell-Evans-Polanyi (BEP) relations, volcano plots, Tafel slopes, the Butler-Volmer equation, and other linear free energy relations (LFERs), which all depend on the implicit assumption that the active sites are “similar” and that surface adsorption is close to ideal. These assumptions underly the ubiquitous intuition based on the Sabatier Principle, that the fastest catalysis will occur when key intermediates have free energies of adsorption that are not too strong nor too weak. Current catalysis research often aims to minimize the complexity of non-ideal isotherms through experimental and computational design (e.g., the use of single crystal surfaces), and these studies are the foundation of the field. In contrast, this Perspective argues that the heterogeneity of binding sites and binding energies is an inherent strength of these catalysts. Here, this diversity makes many nanoscale catalysts inherently a high-throughput screen wrapped in a tiny package. Only by making the heterogeneity part of the foundation of catalysis models, sorting the types of active sites and dissecting non-ideal binding isotherms, will modern catalysis learn to harness the inherent diversity of real catalysts. Controlling and exploiting diversity rather than avoiding it will help to optimize complex modern catalysts and catalytic conditions.

Mayer, James M.↗