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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 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Programmable nanowrinkle-induced room-temperature exciton localization in monolayer WSe2

Abstract Localized states in two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been the subject of intense study, driven by potential applications in quantum information science. Despite the rapidly growing knowledge surrounding these emitters, their microscopic nature is still not fully understood, limiting their production and application. Motivated by this challenge, and by recent theoretical and experimental evidence showing that nanowrinkles generate strain-localized room-temperature emitters, we demonstrate a method to intentionally induce wrinkles with collections of stressors, showing that long-range wrinkle direction and position are controllable with patterned array design. Nano-photoluminescence (nano-PL) imaging combined with detailed strain modeling based on measured wrinkle topography establishes a correlation between wrinkle properties, particularly shear strain, and localized exciton emission. Beyond the array-induced wrinkles, nano-PL spatial maps further reveal that the strain environment around individual stressors is heterogeneous due to the presence of fine wrinkles that are less deterministic. At cryogenic temperatures, antibunched emission is observed, confirming that the nanocone-induced strain is sufficiently large for the formation of quantum emitters. At 300 K, detailed nanoscale hyperspectral images uncover a wide range of low-energy emission peaks originating from the fine wrinkles, and show that the states can be tightly confined to regions <10 nm, even in ambient conditions. These results establish a promising potential route towards realizing room temperature quantum emission in 2D TMDC systems.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways

Solid-liquid interfaces are at the heart of many modern-day technologies and provide a challenge to many materials simulation methods. A realistic first-principles computational study of such systems entails the inclusion of solvent effects. In this work, we implement an implicit solvation model that has a firm theoretical foundation into the widely used density-functional code Vienna ab initio Software Package. The implicit solvation model follows the framework of joint density functional theory. We describe the framework, our algorithm and implementation, and benchmarks for small molecular systems. We apply the solvation model to study the surface energies of different facets of semiconducting and metallic nanocrystals and the S N 2 reaction pathway. We find that solvation reduces the surface energies of the nanocrystals, especially for the semiconducting ones and increases the energy barrier of the S N 2 reaction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Scoreboard

Emerging HPC machines have given rise to enhanced compute power that far outstrips the machine's ability to save large scale results for post-processing. To combat this, in situ data analysis techniques are slowly being adopted. With in situ data management favoring workflows composed of multiple simulations and analyses connected in transit on heterogeneous machines, scientists and engineers need a tool that enables them to create data extracts, visualizations, and interactively monitor and steer their simulations. Scoreboard Phase II is a next generation analysis software that supports composite in transit workflows on heterogeneous architectures and restores interactivity to in situ data analysis through simulation monitoring and computational steering. Scoreboard provides a simulation dashboard with graphs of metrics over time, controls for setting custom simulation steering parameters, controls for managing the set of data extracts being produced in the simulation, as well as the ability to explore data extracts, all from a web browser. Realizing the vision outlined in this project required research into making a system that integrates end to end from simulations all the way to the user. In situ tools generally suffer from complexity and excessive software dependencies. Scoreboard, by contrast, is easy to build and integrate into simulation codes and it provides first class FORTRAN support. The Scoreboard library is capable of in situ and in transit data analysis that can produce data extracts commonly needed for Computational Fluid Dynamics (CFD) analysis. Simulations can transparently stage data in transit to a Scoreboard Endpoint program, which can accept their data and produce the requested data extracts. This lets simulations return to their work while the Endpoint works on the analysis. Efficiently staging the data at scale was a topic of this research. Scoreboard provides the means to let the user manage data extracts and monitor/steer many simulations from a web browser. This area of the research focused on discovery of in transit network components to expose and control their steering parameters within an interactive browser-based user interface that includes: system topology, gathered metrics, notifications, dynamically-generated steering controls, and exploration of visualization data products.

Whitlock, BradJoseph [Intelligent Light] (00000001↗
DOE OSTI2018

Synthesizing models useful for ecohydrology and ecohydraulic approaches: An emphasis on integrating models to address complex research questions

Ecohydrology combines empiricism, data analytics, and the integration of models to characterize linkages between ecological and hydrological processes. A challenge for practitioners is determining which models best generalizes heterogeneity in hydrological behaviour, including water fluxes across spatial and temporal scales, integrating environmental and socio–economic activities to determine best watershed management practices and data requirements. We conducted a literature review and synthesis of hydrologic, hydraulic, water quality, and ecological models designed for solving interdisciplinary questions. We reviewed 1,275 papers and identified 178 models that have the capacity to answer an array of research questions about ecohydrology or ecohydraulics. Of these models, 43 were commonly applied due to their versatility, accessibility, user–friendliness, and excellent user–support. Forty–one of 43 reviewed models were linked to at least 1 other model especially: Water Quality Analysis Simulation Program (linked to 21 other models), Soil and Water Assessment Tool (19), and Hydrologic Engineering Center's River Analysis System (15). However, model integration was still relatively infrequent. There was substantial variation in model applications, possibly an artefact of the regional focus of research questions, simplicity of use, quality of user–support efforts, or a limited understanding of model applicability. Simply increasing the interoperability of model platforms, transformation of models to user–friendly forms, increasing user–support, defining the reliability and risk associated with model results, and increasing awareness of model applicability may promote increased use of models across subdisciplines. Furthermore, the current availability of models allows an array of interdisciplinary questions to be addressed, and model choice relates to several factors including research objective, model complexity, ability to link to other models, and interface choice.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Interfaces of dicationic ionic liquids and graphene: a molecular dynamics simulation study

Molecular dynamics simulations were performed to investigate the interfacial structure and capacitance of electrical double layers (EDLs) in dicationic ionic liquids (DILs) 1-alkyl-3-dimethylimidazolium tetrafluoroborate [Cn(mim)2](BF4)2 (n = 3, 6, 9), with respect to a baseline of a monocationic ionic liquid [C3mim][BF4], near planar carbon electrodes consisting of graphene sheets. The simulation results show that an adsorbed layer with double peaks is exclusively found for [C3(mim)2](BF4)2, while a single peak of the other three cations is observed at the neutral electrode, due to the difference in ion–wall interaction and cation–anion association. As the electrode becomes negatively charged, the second peak of [C3(mim)2]2+ is dramatically reduced, whereas those of [C6(mim)2]2+ and [C9(mim)2]2+ become non-trivial. The capacitance–potential curve of EDLs in DILs manifests a transition from camel shape to bell shape as the cation chain length increases, which is attributed to the enlargement of ion adsorption (per unit charge) on the electrode and the decrease of attractive interaction between ions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Localization of proteins involved in the biogenesis and repair of the photosynthetic apparatus to thylakoid subdomains in Arabidopsis

Abstract Thylakoid membranes in chloroplasts and cyanobacteria harbor the multisubunit protein complexes that catalyze the light reactions of photosynthesis. In plant chloroplasts, the thylakoid membrane system comprises a highly organized network with several subcompartments that differ in composition and morphology: grana stacks, unstacked stromal lamellae, and grana margins at the interface between stacked and unstacked regions. The localization of components of the photosynthetic apparatus among these subcompartments has been well characterized. However, less is known about the localization of proteins involved in the biogenesis and repair of the photosynthetic apparatus, the partitioning of proteins between two recently resolved components of the traditional margin fraction (refined margins and curvature), and the effects of light on these features. In this study, we analyzed the partitioning of numerous thylakoid biogenesis and repair factors among grana, curvature, refined margin, and stromal lamellae fractions of Arabidopsis thylakoid membranes, comparing the results from illuminated and dark‐adapted plants. Several proteins previously shown to localize to a margin fraction partitioned in varying ways among the resolved curvature and refined margin fractions. For example, the ALB3 insertase and FtsH protease involved in photosystem II (PSII) repair were concentrated in the refined margin fraction, whereas TAT translocon subunits and proteins involved in early steps in photosystem assembly were concentrated in the curvature fraction. By contrast, two photosystem assembly factors that facilitate late assembly steps were depleted from the curvature fraction. The enrichment of the PSII subunit OE23/PsbP in the curvature fraction set it apart from other PSII subunits, supporting the previous conjecture that OE23/PsbP assists in PSII biogenesis and/or repair. The PSII assembly factor PAM68 partitioned differently among thylakoid fractions from dark‐adapted plants and illuminated plants and was the only analyzed protein to convincingly do so. These results demonstrate an unanticipated spatial heterogeneity of photosystem biogenesis and repair functions in thylakoid membranes and reveal the curvature fraction to be a focal point of early photosystem biogenesis.

Chotewutmontri, Prakitchai↗
DOE OSTI2022

Importance of interface open circuit potential on aqueous hydrogenolytic reduction of benzyl alcohol over Pd/C

Abstract The open circuit potential (OCP) established by the quasi-equilibrated electrode reaction of H 2 and H 3 O + (hydr.) , complicates catalytic reactions significantly. The hydrogenolysis rate of benzylic alcohol on Pd/C increases 2-3 orders of magnitude with the pH decreasing from 7 to 0.6. The reaction follows a pathway of protonated benzyl alcohol dehydration to a benzylic carbenium ion, followed by a hydride addition to form toluene. The dehydration of protonated benzyl alcohol is kinetic relevent, thus, being enhanced at lower pH. The OCP stabilizes all cationic species in the elementary steps. Particularly, the initial state (benzyl alcohol oxonium ion) is less stabilized than the dehydration transition state and the product (benzylic carbenium), thus, lowering the free energy barrier of the rate-determining step. In accordance, the rate increased with increasingly negative OCP. Beside OCP, an external negative electric potential in an electrocatlaytic system was also demonstrated to enhance the rate in the same way.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

History-dependent ion transport through conical nanopipettes and the implications in energy conversion dynamics at nanoscale interfaces

The dynamics of ion transport at nanostructured substrate–solution interfaces play vital roles in high-density energy conversion, stochastic chemical sensing and biosensing, membrane separation, nanofluidics and fundamental nanoelectrochemistry. Advancements in these applications require a fundamental understanding of ion transport at nanoscale interfaces. The understanding of the dynamic or transient transport, and the key physical process involved, is limited, which contrasts sharply with widely studied steady-state ion transport features at atomic and nanometer scale interfaces. Here we report striking time-dependent ion transport characteristics at nanoscale interfaces in current–potential (I–V) measurements and theoretical analyses. First, a unique non-zero I–V cross-point and pinched I–V curves are established as signatures to characterize the dynamics of ion transport through individual conical nanopipettes. Moreoever, ion transport against a concentration gradient is regulated by applied and surface electrical fields. The concept of ion pumping or separation is demonstrated via the selective ion transport against concentration gradients through individual nanopipettes. Third, this dynamic ion transport process under a predefined salinity gradient is discussed in the context of nanoscale energy conversion in supercapacitor type charging–discharging, as well as chemical and electrical energy conversion. Our analysis of the emerging current–potential features establishes the urgently needed physical foundation for energy conversion employing ordered nanostructures. The elucidated mechanism and established methodology can be generalized into broadly-defined nanoporous materials and devices for improved energy, separation and sensing applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Orientation Relationships of Pure Tin on Single Crystal Germanium Substrates

The limited number of independent β-Sn grain orientations resulting from the difficulty in nucleating β-Sn during solidification of Sn-based solders has a large effect on the resulting β-Sn grain size and, hence, on overall solder joint performance and reliability. This study analyzes the efficacy of Ge as a heterogeneous nucleation agent for β-Sn by observing the morphologies and orientation relationships of as-deposited, solid-state annealed, and liquid-state annealed pure Sn films on single crystal Ge (100), (110), and (111) substrates. Here, the results from scanning electron microscopy and electron backscatter diffraction showed that the as-deposited Sn films all deposited with a Sn (001)|| z-axis texture, regardless of the underlying Ge substrate orientation. Solid-state annealing at 150 °C for 5 min did not result in significant dewetting of the Sn films, and the films maintained their as-deposited texture of Sn (001)|| z-axis, regardless of the underlying Ge substrate orientation. Liquid-state annealing at 235 °C for 1 min resulted is large-scale dewetting of the Sn films and re-orientation of the Sn films on the various Ge substrates. After solidification, the Ge (100) and (110) single crystal substrates produced patches of dewetted grains of the same orientation but there were no consistent Sn grain textures after liquid-state annealing, suggesting no single orientation relationship. In contrast, solidification on Ge (111) single crystal substrates resulted in isolated grains with a single Sn film texture and an orientation relationship of (100) Sn ∥(111) Ge and [100] Sn ∥[110] Ge . Density Functional Theory simulations of the experimentally observed Ge (111) sample orientation relationship and the Ge/Sn cube-on-cube orientation relationship suggest favorable relative interfacial binding energies for both interface orientations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Enhanced Catalysis under 2D Silica: A CO Oxidation Study

Interfacially confined microenvironments have recently gained attention in catalysis, as they can be used to modulate reaction chemistry. The emergence of a 2D nanospace at the interface between a 2D material and its support can promote varying kinetic and energetic schemes based on molecular level confinement effects imposed in this reduced volume. We report on the use of a 2D oxide cover, bilayer silica, on catalytically active Pd(111) undergoing the CO oxidation reaction. We “uncover” mechanistic insights about the structure-activity relationship with and without a 2D silica overlayer using in situ IR and X-ray spectroscopy and mass spectrometry methods. We find that the CO oxidation reaction on Pd(111) benefits from confinement effects imposed on surface adsorbates under 2D silica. Finally, this interaction results in a lower and more dispersed coverage of CO adsorbates with restricted CO adsorption geometries, which promote oxygen adsorption and lay the foundation for the formation of a reactive surface oxide that produces higher CO 2 formation rates than Pd alone.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Direct and Sensitive Electrochemical Evaluation of Pramipexole Using Graphitic Carbon Nitride (gCN) Sensor

Pramipexole (PMXL) belongs to the benzothiazole class of aromatic compounds and is used in treating Parkinson’s disease; however, overdosage leads to some abnormal effects that could trigger severe side effects. Therefore, it demands a sensitive analytical tool for trace level detection. In this work, we successfully developed an electrochemical sensor for the trace level detection of PMXL, using the voltammetric method. For the analysis, graphitic carbon nitride (gCN) was opted and synthesized by using a high-temperature thermal condensation method. The synthesized nanoparticles were employed for surface characterization, using transmission electron microscopy (TEM), X-ray diffraction (XRD), and atomic force microscopy (AFM) techniques. The electrochemical characterization of the material was evaluated by using the electrochemical impedance spectroscopy (EIS) technique to evaluate the solution–electrode interface property. The cyclic voltammetry (CV) behavior of PMXL displayed an anodic peak in the forward scan, indicating that PMXL underwent electrooxidation, and an enhanced detection peak with lower detection potential was achieved for gCN-modified carbon paste electrode (gCN·CPE). The influence of different parameters on the electrochemical behavior was analyzed, revealing the diffusion governing the electrode process with an equal number of hydronium ions and electron involvement. For the fabricated gCN·CPE, good linearity range was noticed from 0.05 to 500 µM, and a lower detection limit (L D ) of 0.012 µM was achieved for the selected concentration range (0.5 to 30 µM). Selectivity of the electrode in PMXL detection was investigated by conducting an interference study, while the tablet sample analysis demonstrates the sensitive and real-time application of the electrode. The good recovery values for the analysis illustrate the efficiency of the electrode for PMXL analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Scalable synthesis of supported catalysts using fluidized bed atomic layer deposition

Overcoating layers deposited on the surface of heterogeneous catalysts using atomic layer deposition (ALD) have been shown to increase catalyst activity, lifetime, and selectivity. In this study, we performed Al 2 O 3 ALD and Pd ALD in a commercial fluidized bed reactor on high surface area mesoporous powder supports to create overcoated catalysts with high precursor utilization. We investigated the reaction mechanism for both Al 2 O 3 ALD and Pd ALD using in situ mass spectrometry and developed a mathematical model to understand the precursor saturation behaviors. We characterized the catalyst samples using a variety of techniques to measure the surface area, porosity, composition, and surface chemistry of the overcoated catalysts. Finally, we used propane dehydrogenation as a probe reaction to evaluate the performance of the catalysts prepared by fluidized bed ALD.

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

Chromium Tolerant, Highly Active and Stable Electrocatalytic Internal Surface Coating for Cathode of Commercial SOFCs (Final Report)

This project is aimed to develop a chromium (Cr) tolerant, highly active, and stable coating layer on the internal surfaces of the porous composite cathode from commercially available SOFCs. Such coating layer was developed using the additive manufacturing process of Atomic Layer Deposition (ALD) and has been applied on the cathode consisting of either an electronic conductor of LaxSr 1-x MnyO 3-δ (LSM) or mixed ionic and electronic conducting La x Sr 1-x Co y Fe 1-y O 3-δ (LSCF). PI's work has demonstrated that the internal surface of cathode from the commercial cells, can be further tailored using ALD coating to dramatically enhance the cell performance. For instance, ALD layer consisting heterostructured nano composite of nano-Pt and nano-(Mn 0.8 Co 0.2 ) 3 O 4 oxide on the internal surface of porous LSM/YSZ cathode from SOFCs, has resulted in the large reduction of the cell polarizations resistance by up to 53%, and enormous increase of power density over 370%. For the cells with LSCF/Sm 2 O 3 doped CeO 2 (SDC) cathode, the conformal layer of nano-composite consisting of superjacent CoOx and subjacent minimum amount of Pt nano-grains has resulted in the power density enhancement by 126% for the large scale industry tubular cells at 750°C, and both the performance enhancement and nanostructure of the ALD layer are stable over ~ 2000 h continuous operation performed at industry test station. In the meanwhile, those ALD coating layer developed by PI's work is also inherently Cr-tolerant, and could act as physical barrier for preventing Cr diffusion into the cathode backbone, so as to mitigate the Cr poisoning effect on the cathode. In this project, the impact of Cr on the performance of those ALD coated commercial cells has been evaluated. Based on evolution of the cell performance, the ALD coating layer chemistry and ALD coating layer thickness has been optimized to maximize the overall Cr tolerance, cell power density and cell longevity. Different ALD coating has been applied onto the internal surface of LSM/YSZ and LSCF/SDC backbone respectively. The architecture/scaffold structures on the internal surface of different cathode, designed by this project, was catalogued and analyzed using High Resolution Transmission Electron Microscopy (HRTEM), and cell power/durability performance are assured via comprehensive electrochemical performance testing in the industry operation relevant conditions. The impact of the electrochemical operation current density, the water humidity, the cell operation temperature, and cell operation duration on the Cr tolerance of ALD coated cells has been systematically investigated. There is completely different nanostructure degradation mechanisms between LSM and LSCF cells induced by Cr contamination. For the LSCF/SDC baseline cell, With the Cr source, there is no apparent Sr surface segregation phase even for the baseline cell operated for 3000 h at 750 °C. With the Cr source, there is significant amorphous (SrCr)Ox phase accumulated in the original pore region. For the commercial baseline cells, Cr contaminants on the LSM electrode severely impacted the entire cell's electrochemical performance and nanostructure degradation. Those degradations include (1). Peak power density loss of 64 % after 109 h of operation. The dramatic increase in Rp (2). They are cracking at LSM/SSZ interface, LSM grains. SSZ remains intact but with (CrMn)Ox. By contrast, ALD coating (MnCo)Ox/Pt dramatically improves the Cr resistance, as follows (1). ALD-coated cell with a power density is 280-380 % of the baseline cell, depending on the ALD layer thickness. (2). For a cell with a 20 nm thick ALD layer, there is a large performance enhancement (> 200 % power density) induced by ALD coating of Cr-tolerant Mn 0.8 Co 0.2 Ox. (3). For a cell with a 20 nm thick ALD layer, after 168 h at 750 °C power density of the ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination for 109 h. The ALD coating on the internal surface of cathode developed by this project integrated multi-functions. Those multi-functions include (1). Dramatically improving the cell power density for the commercial cells; (2). Dramatically improving contamination resistance of the cathode, for being an excellent protection coating layer sealing off Cr contamination. (3). Dramatically increasing the cell longevity by potentially preventing the microstructure evolution and grain coarsening of the cathode. Overall, this project will provide a simple solution to simultaneously enhance power density and increase the reliability, robustness, and endurance of commercial SOFCs, over the entire operating temperature range of 650-800 °C. For the inherently functional SOFC, the ALD coating of LSM based cathode mitigate the Cr-contamination. Power density of ALD-coated cell is ~ 600% of that baseline cell upon operation with Cr contamination. In addition to SOFCs, the novel on-demand design approach and creation of multifunctional heterogeneous architecture on the electrode surface presented in this work opens further research for their application in other types of fuel cells, batteries, and sensors for which electrochemical reactions on the surface are similarly critical.

36 MATERIALS SCIENCE↗
DOE OSTI2016

A Generic Model for Electric Double Layers in Porous Electrodes

The performance of electric-double-layer capacitors (EDLCs) hinges on microscopic charge distributions near the electrode/electrolyte interfaces. Whereas practical EDLCs consist of electrodes made of amorphous porous materials, theoretical understanding of EDLCs is mostly based on EDL structure near a planar surface or on simplistic models that have little relevance to realistic systems. In this work, we propose a spherical shell model to account for both pore size and curvature effects of amorphous porous materials. The EDL structure in spherical shells has been investigated over a broad range of pore sizes and curvatures by use of classic density functional theory. Theoretical results reveal that the curvature effects on convex and concave EDLs are drastically different and that materials with extensive convex surfaces will lead to maximized capacitance. Like a slit pore, the spherical shell model also predicts oscillatory variation of capacitance with pore size, but the oscillatory behavior is magnified as the curvature increases. The joint effects of pore size and curvature identified in this work give new insight into materials design for porous electrodes with optimal EDLC performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Symmetry in Seeded Metal Nanocrystal Growth

Symmetry underpins the structure and function of the world around us and is also captured in modern nanomaterials, where changing the symmetry of a nanocrystal or the interparticle spacing and orientation of nanocrystal building blocks in a superlattice can give new function. However, the synthesis and assembly of nanocrystals have been limited largely to simple compositions and structures. It remains a grand challenge to achieve nanocrystals with compositional and structural complexity while maintaining the monodispersity required for their use. This Account will illustrate through recent examples that seeded methods enable the synthesis of compositionally and structurally complex multimetallic crystals with defined and predictable symmetries for applications in plasmonics and catalysis. This outcome arises because the barrier for heterogeneous nucleation (i.e., seeded) is lower than that of homogeneous nucleation, where seeds can serve as preferential sites for the growth of complex structures and crystal phases. Our analysis begins by considering metal overgrowth from single-crystalline seeds of different shapes and symmetries, where the kinetics of adatom addition to seeds relative to their diffusion across seeds accounts for the expressed nanocrystal shapes. These results are then compared to overgrowth from seeds with different internal structures (i.e., planar defects), where the relationships between nanocrystal size and volumetric strain energy and surface energy are discussed. A major finding from this analysis is that often the underlying symmetry of seeds can be predictably transferred to the final crystals during overgrowth processes. Consequences of this finding are the predictable syntheses of crystals with different hierarchies akin to snowcrystals as well as nanocrystals with complex compositions (e.g., quaternary nanoparticles). Yet, there are subtle aspects to seeded growth that pave a path toward examples where nanocrystal symmetry has been reduced compared to the original seeds in a controlled manner. As we found, both the concentrations of metal precursors and capping agents can impact whether symmetry is transferred or reduced during overgrowth. Examples from our laboratory will be placed in context to other reported strategies for symmetry breaking. As will be argued, understanding what conditions favor symmetry preservation versus symmetry reduction during seeded crystal growth is central to accessing next-generation crystal forms. The Account concludes by outlining synthetic challenges associated with forming nanoscale heterostructures with precise 3-D placement of different materials within a given nanocrystal as well as facet control within different material domain and interface engineering. Furthermore, we envision meeting these challenges through regioselective and chemoselective seeded syntheses for which a foundation is outlined herein.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Large bandgap observed on the surfaces of EuZn 2 As 2 single crystals

EuM 2 As 2 (M = Zn, Cd, In, Sn etc.) is an excellent material system for studying magnetism-tuned topological properties. However, discrepancies exist between experimental data and theoretical calculations regarding the bulk and surface bandgaps. In this work, cleaved EuZn 2 As 2 crystals are studied using scanning tunneling microscopy/spectroscopy and density functional theory calculations. Triangular-shaped defect-induced modifications in the local density of states help distinguish between Eu-terminated and AsZn-terminated surfaces. While large bandgaps (~1.5 eV at 77 K) are observed on both pristine surfaces, the bandgap size is found to be highly sensitive to local heterogeneity, tending to decrease. By combining experimental observations with theoretical simulations, we conclude that the reduced bandgap in heterogeneous regions arises from Zn vacancies and/or substitution by As atoms, both impacting greater in the Eu surface electronic properties than those in the AsZn surface. This demonstrates the intimate relationship between the electronic structure and magnetism in EuZn 2 As 2 .

interfaces↗
DOE OSTI2020

Determining the hydration energetics on carbon-supported Ru catalysts: An adsorption calorimetry and density functional theory study

Fundamental knowledge on the energetics at the interface between a water layer and a metal catalyst is essential so as to understand the roles that water can play in the synthesis, activation and regeneration of noble metal-based catalysts. Here, we report the direct measurement of the enthalpy of water adsorption (Δh ads ) on activated carbon (C) and activated C-supported Ru nanoparticles, which are promising catalyst as applied to the hydrogenation/hydrodeoxygenation (HDO) of oxygenates (phenolics, aldehydes, etc.). Specifically, the near-zero coverage enthalpy of water adsorption on a C-supported Ru catalyst is -75.3 ± 0.4 kJ/(mol water), suggesting favorable water–metal binding. This is much more exothermic than that on C, which has an enthalpy of adsorption of -50.3 ± 1.3 kJ/(mol water). Despite the favorable initial binding, the magnitudes of enthalpies of water condensation on C and Ru-C indicate that overall, their surfaces are both hydrophobic. Moreover, the experimentally-measured near-zero coverage water adsorption enthalpy at the Ru sites is in very good agreement with our density functional theory based calculations. At low coverages, we obtain a water binding energy of -61.7 kJ/(mol water), which increases to -78.1 kJ/(mol water) at saturation. Complementary results are also obtained from a thermal analysis, which employed a thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TG-DSC-MS), a spectroscopic investigation using ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a morphological evaluation with transmission electron microscopy (TEM). We point out that in carbon-supported metal catalysts, such as Ru-C, a strong hydration at near-zero coverage and relative weak water-surface interactions occurs upon saturation. Such heterogeneity is essential and crucial for catalytic hydrogenation/HDO reactions that involve balanced interactions among the water-rich reactant mixture and nonpolar organic products.

09 BIOMASS FUELS↗