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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
NASA NTRS2001

Controlling Growth Orientation of Phthalocyanine Films by Electrical Fields

Organic Phthalocyanine films have many applications ranging from data storage to various non-linear optical devices whose quality is affected by the growth orientation of Phthalocyanine films. Due to the structural and electrical properties of Phthalocyanine molecules, the film growth orientation depends strongly on the substrate surface states. In this presentation, an electrical field up to 4000 V/cm is introduced during film growth. The Phthalocyanine films are synthesized on quartz substrates using thermal evaporation. An intermediate layer is deposited on some substrates for introducing the electrical field. Scanning electron microscopy, x-ray diffraction, and Fourier transform infrared spectroscopy are used for measuring surface morphology, film structure, and optical properties, respectively. The comparison of Phthalocyanine films grown with and without the electrical field reveals different morphology, film density, and growth orientation, which eventually change optical properties of these films. These results suggest that the growth method in the electrical field can be used to synthesized Phthalocyanine films with a preferred crystal orientation as well as propose an interaction mechanism between the substrate surface and the depositing molecules. The details of growth conditions and of the growth model of how the Phthalocyanine molecules grow in the electrical field will be discussed.

Zhu, S.↗
DOE OSTI2020

Mercury methylation potential in a sand dune on Lake Michigan's eastern shoreline

Lake Michigan hosts the largest freshwater sand dune system in the world and is economically important for the fishery industry and tourism. Due to industrial pollution and atmospheric mercury (Hg) deposition, toxic levels of methylmercury (MeHg) have been found in the Lake biota, but little information is known regarding MeHg sources and Hg methylation potential in the shoreline sand dunes. In this study, we conducted anaerobic incubation experiments with beach sands collected from Ludington, Michigan, and examined the effects of organic carbon substrate addition, inorganic nitrogen, and mineral magnetite on Hg methylation. Despite nutrient poor and low-organic carbon conditions, appreciable Hg methylation activity coupled with carbon degradation was observed in the sands. Addition of acetate as a carbon source substantially increased MeHg production from 2 to 380 ng/kg sediment while acetate was rapidly degraded in the first 19 days of incubation. Ammonium addition showed little influence on carbon degradation or Hg methylation, whereas iron oxide addition (~1% dry weight) significantly inhibited both carbon degradation and MeHg production (by up to 90%), highlighting strongly coupled interactions between microbes, carbon substrates, and minerals. This research demonstrates the potential of microbial Hg methylation in the sand dunes, which may play a role in MeHg input and bioaccumulation in the Lake Michigan ecosystem.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Underlying Substrate Effect on Electrochemical Activity for Hydrogen Evolution Reaction with Low‐Platinum‐Loaded Catalysts

Platinum is known as the best catalyst for the hydrogen evolution reaction (HER) but the scarcity and high cost of Pt limit its widespread applicability. Herein, the role of the underlying substrate on the HER activity of dispersed Pt atoms is uncovered. A direct current magnetron sputtering technique is utilized to deposit transition metal (TM) thin films of W, Ti, and Ta as underlying substrates for extremely low loading of Pt (<1.5 at%). The electrocatalytic performance of as‐synthesized samples for the HER is examined in both alkali and acidic media. The results show that despite the low loading of Pt, the Pt/TM catalysts produce hydrogen at a rate comparable to that of pristine bulk Pt. Pt/TM catalysts also display good stability with less than 5% decay in performance after 10 h of continuous HER operation. Based on the computational study, the excellent performance is attributed to the modified electronic properties of the Pt atoms, offering ideal binding energy for HER due to interaction with the underlying substrates. This work provides a robust and industry‐friendly route toward designing efficient catalytic systems for important electrochemical reactions such as HER and others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Merging a mechanistic enzymatic model of soil heterotrophic respiration into an ecosystem model in two AmeriFlux sites of northeastern USA

Heterotrophic respiration (Rh), microbial processing of soil organic matter to carbon dioxide (CO 2 ), is a major, yet highly uncertain, carbon (C) flux from terrestrial systems to the atmosphere. Temperature sensitivity of Rh is often represented with a simple Q 10 function in ecosystem models and earth system models (ESMs), sometimes accompanied by an empirical soil moisture modifier. More explicit representation of the effects of soil moisture, substrate supply, and their interactions with temperature has been proposed as a way to disentangle the confounding factors of apparent temperature sensitivity of Rh and improve the performance of ecosystem models and ESMs. The objective of this work was to insert into an ecosystem model a more mechanistic, but still parsimonious, model of environmental factors controlling Rh and evaluate the model performance in terms of soil and ecosystem respiration. The Dual Arrhenius and Michaelis-Menten (DAMM) model simulates Rh using Michaelis-Menten, Arrhenius, and diffusion functions. Soil moisture affects Rh and its apparent temperature sensitivity in DAMM by regulating the diffusion of oxygen, soluble C substrates, and extracellular enzymes to the enzymatic reaction site. Here, we merged the DAMM soil flux model with a parsimonious ecosystem flux model, FöBAAR (Forest Biomass, Assimilation, Allocation and Respiration). We used high-frequency soil flux data from automated soil chambers and landscape-scale ecosystem fluxes from eddy covariance towers at two AmeriFlux sites (Harvard Forest, MA and Howland Forest, ME) in the northeastern USA to estimate parameters, validate the merged model, and to quantify the uncertainties in a multiple constraints approach. The optimized DAMM-FöBAAR model better captured the seasonal and inter-annual dynamics of soil respiration (Soil R) compared to the FöBAAR-only model for the Harvard Forest, where higher frequency and duration of drying events significantly regulate substrate supply to heterotrophs. However, DAMM-FöBAAR showed improvement over FöBAAR-only at the boreal transition Howland Forest only in unusually dry years. The frequency of synoptic-scale dry periods is lower at Howland, resulting in only brief water limitation of Rh in some years. At both sites, the declining trend of soil R during drying events was captured by the DAMM-FöBAAR model; however, model performance was also contingent on site conditions, climate, and the temporal scale of interest. While the DAMM functions require a few more parameters than a simple Q10 function, we have demonstrated that they can be included in an ecosystem model and reduce the model-data mismatch. Moreover, the mechanistic structure of the soil moisture effects using DAMM functions should be more generalizable than the wide variety of empirical functions that are commonly used, and these DAMM functions could be readily incorporated into other ecosystem models and ESMs.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Depinning and nonequilibrium dynamic phases of particle assemblies driven over random and ordered substrates: A review

Here, we review the depinning and nonequilibrium phases of collectively interacting particle systems driven over random or periodic substrates. This type of system is relevant to vortices in type-II superconductors, sliding charge density waves, electron crystals, colloids, stripe and pattern forming systems, and skyrmions, and could also have connections to jamming, glassy behaviors, and active matter. These systems are also ideal for exploring the broader issues of characterizing transient and steady state nonequilibrium flow phases as well as nonequilibrium phase transitions between distinct dynamical phases, analogous to phase transitions between different equilibrium states. We discuss the differences between elastic and plastic depinning on random substrates and the different types of nonequilibrium phases which are associated with specific features in the velocity-force curves, fluctuation spectra, scaling relations, and local or global particle ordering. We describe how these quantities can change depending on the dimension, anisotropy, disorder strength, and the presence of hysteresis. Within the moving phase we discuss how there can be a transition from a liquid-like state to dynamically ordered moving crystal, smectic, or nematic states. Systems with periodic or quasiperiodic substrates can have multiple nonequilibrium second or first order transitions in the moving state between chaotic and coherent phases, and can exhibit hysteresis. We also discuss systems with competing repulsive and attractive interactions, which undergo dynamical transitions into stripes and other complex morphologies when driven over random substrates. Throughout this work we highlight open issues and future directions such as absorbing phase transitions, nonequilibrium work relations, inertia, the role of non-dissipative dynamics such as Magnus effects, and how these results could be extended to the broader issues of plasticity in crystals, amorphous solids, and jamming phenomena.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Collective transport for active matter run-and-tumble disk systems on a traveling-wave substrate

Here, we examine numerically the transport of an assembly of active run-and-tumble disks interacting with a traveling-wave substrate. We show that as a function of substrate strength, wave speed, disk activity, and disk density, a variety of dynamical phases arise that are correlated with the structure and net flux of disks. We find that there is a sharp transition into a state in which the disks are only partially coupled to the substrate and form a phase-separated cluster state. This transition is associated with a drop in the net disk flux, and it can occur as a function of the substrate speed, maximum substrate force, disk run time, and disk density. Since variation of the disk activity parameters produces different disk drift rates for a fixed traveling-wave speed on the substrate, the system we consider could be used as an efficient method for active matter species separation. Within the cluster phase, we find that in some regimes the motion of the cluster center of mass is in the opposite direction to that of the traveling wave, while when the maximum substrate force is increased, the cluster drifts in the direction of the traveling wave. This suggests that swarming or clustering motion can serve as a method by which an active system can collectively move against an external drift.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Influence of Hydronium Ions in Zeolites on Sorption

Abstract In the presence of sufficient concentrations of water, stable, hydrated hydronium ions are formed in the pores and at the surface of solid acids such as zeolites. For a medium‐pore zeolite, such as zeolite MFI, hydrated hydronium ions consist of eight water molecules and have an effective volume of 0.24 nm 3 . In their presence, larger organic molecules can only adsorb in the portions of the pore that are not occupied by hydronium ions. As a consequence, the available pore volume decreases proportionally to the concentration of the hydronium ions. The higher charge density (the increasing ionic strength) that accompanies an increasing concentration of hydronium ions leads to an increase in the activity coefficients of the adsorbed substrates, thus, weakening the interactions between the organic part of the molecules and the zeolite and favoring the interactions with polar groups. The quantitative understanding of these interactions makes it possible to link a collective property such as hydrophilicity and hydrophobicity of zeolites to specific interactions on molecular level.

Eckstein, Sebastian↗
DOE OSTI2017

Surfactant-assisted stabilization of Au colloids on solids for heterogeneous catalysis

Here, the stabilization of surfactant-assisted synthesized colloidal noble metal nanoparticles (NPs, e.g., Au NPs) on solids is a promising strategy for preparing supported nanocatalysts for heterogeneous catalysis because of their uniform particle sizes, controllable shapes, and tunable compositions. However, the removal of surfactants to obtain clean surfaces for catalysis through traditional approaches (e.g., solvent extraction and thermal decomposition) can easily induce the sintering of NPs, greatly hampering their use in synthesis of novel catalysts. Herein, we demonstrate that such unwanted surfactants can be utilized to stabilize NPs on solids via a simple yet efficient thermal annealing strategy. After being annealed in N 2 flow, the surface-bound surfactants are in situ carbonized as sacrificial architectures that form a conformal coating on NPs and assist in creating an enhanced metal-support interaction between NPs and substrate, thus slowing down the Ostwald ripening process during post-oxidative calcination to remove surface covers.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Nonreciprocal spin-wave propagation in YIG/GGG: a limit on the DMI parameter

Materials with low damping, such as Yttrium Iron Garnet (YIG), are of interest in connection with spintronic devices. A promising structure for information storage is the Skyrmion, a domain wall quasi-particle. It has been shown that the stabilization of a Skyrmion can be energetically favorable with the addition of spin-orbit coupling (SOC) through the Dzyaloshinsky-Moriya Interaction (DMI). This interaction should be largest in metals, but still present in insulators. In order to produce spintronic devices using YIG, we must evaluate the DMI interaction inherent in the substrate used to grow the YIG, which is generally Gadolinium Gallium Garnet (GGG). In this study, we measure nonreciprocal spin wave propagation in a thick YIG film in order to place a limit on the DMI parameter in a YIG/GGG bilayer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

A Model for the Characterization of the Polarizability of Thin Films Independently of the Thickness of the Film

It is known that the dielectric properties of thin films can be modified relative to the bulk material because the interaction between film and substrate influences the mobility of the atoms or molecules in the first layers. Here we show that a strong scale effect occurs in nanometer size octadecylammine thin films. Here, this effect is attributed to the different distribution of molecules depending on the size of the film. To accurately describe this effect, we have developed a model which is a reinterpretation of the linearized Thomas-Fermi approximation. Within this model, we have been able to characterize the polarizability of thin films independently of the thickness of the film.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Pb Sorption at the Barite (001)–Water Interface

Sorption of ions at the mineral-water interface is an important factor that determines the fate of toxic metals in the environment. Here, we use barite as a model substrate to understand the interaction of toxic-metal lead (Pb) with ionic crystals. The coverage and location of Pb sorbed to the (001) surface was measured as a function of aqueous Pb concentration ([Pb] aq ) using in situ specular resonant anomalous X-ray reflectivity (RAXR) to determine the sorption capacity and process. In this work, the results show that Pb sorption occurs via incorporation (primarily within the top barite layer similar to 3 angstrom in depth) and adsorption (mostly as an inner-sphere complex at similar to 2 angstrom in height) simultaneously. Both the incorporated and adsorbed Pb coverages increase with increasing [Pb] aq up to [Pb] aq similar to 200 mu M, above which the adsorbed fraction increases more rapidly than the incorporated fraction. This enhanced adsorption has a height distribution that is further extended (>= 15 angstrom from the surface) than that observed in lower [Pb] aq . This change in distribution is interpreted as arising from additional sorption of outer-sphere species or Pb-bearing phases precipitated on the surface. Desorption experiments in Pb-free solutions show that the incorporated fraction is more resistant to removal than the adsorbed fraction, consistent with the speciation-dependent stabilities premised in the classical sorption models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Flexible Heteroepitaxy of CoFe 2 O 4 /Muscovite Bimorph with Large Magnetostriction

Van der Waals epitaxy was used to fabricate a bimorph composed of ferrimagnetic cobalt ferrite (CoFe 2 O 4 , CFO) and flexible muscovite. The combination of X-ray diffraction and transmission electron microscopy was conducted to reveal the heteroepitaxy of the CFO/muscovite system. The robust magnetic behaviors against mechanical bending were characterized by hysteresis measurements and magnetic force microscopy, which maintain a saturation magnetization (Ms) of ~120–150 emu/cm 3 under different bending states. The large magnetostrictive response of the CFO film was then determined by digital holographic microscopy, where the difference of magnetostrction coefficient (Δλ) is -104 ppm. We attribute the superior performance of this bimorph to the nature of weak interaction between film and substrate. Such a flexible CFO/muscovite bimorph provides a new platform to develop next-generation flexible magnetic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Principles of Design for Substrate-Supported Molecular Switches Based on Physisorbed and Chemisorbed States

The physisorbed (precursor) and chemisorbed states of a molecule on metal surfaces can be utilized to build a logic switch at the single-molecule level, enabling further microminiaturization of electronic devices beyond the silicon limits. However, a serious drawback of this design is easy lateral diffusion of the molecule in the physisorbed state, which may destroy the normal switch operation. Here, we demonstrate that anchoring engineering can be an effective way to enhance the stability of molecular switches without degrading switching functionality. As exemplified by trans -ADT on Cu(111), we show that the lateral diffusion of such molecular switch can be obstructed by the anchoring of the ending thiophene groups, along with a rotation of the adsorbate during the switching process. More general, our results also suggest that when searching for molecular switches with reversible physisorbed and chemisorbed states with excellent bistability and lateral stability, the focus should be on finding molecules with a moderate HOMO–LUMO energy gap and anchoring atoms with positive charge that can then be deposited on substrates with which they interact moderately. Furthermore, this allows further improvement of the lateral and vertical stability of such a molecular switch by substituting the thiophene groups with selenophene, thus establishing trans -ADS on Cu(111) as a promising switch.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Fabrication of a Microcavity Prepared by Remote Epitaxy over Monolayer Molybdenum Disulfide

We report advances in epitaxy have enabled the preparation of high-quality material architectures consisting of incommensurate components. Remote epitaxy based on lattice transparency of atomically thin graphene has been intensively studied for cost-effective advanced device manufacturing and heterostructure formation. However, remote epitaxy on nongraphene two-dimensional (2D) materials has rarely been studied even though it has a broad and immediate impact on various disciplines, such as many-body physics and the design of advanced devices. Herein, we report remote epitaxy of ZnO on monolayer MoS 2 and the realization of a whispering-gallery-mode (WGM) cavity composed of a single crystalline ZnO nanorod and monolayer MoS 2 . Cross-sectional transmission electron microscopy and first-principles calculations revealed that the nongraphene 2D material interacted with overgrown and substrate layers and also exhibited lattice transparency. The WGM cavity embedding monolayer MoS 2 showed enhanced luminescence of MoS 2 and multimodal emission.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Twenty Years of Progress, Challenges, and Opportunities in Measuring and Understanding Soil Respiration

Abstract Soil respiration (Rs), the soil‐to‐atmosphere flux of CO 2 , is a dominant but uncertain part of the carbon cycle, even after decades of study. This review focuses on progress in understanding Rs from laboratory incubations to global estimates. We survey key developments of in situ ecosystem‐scale Rs observations and manipulations, synthesize Rs meta‐analyses and global flux estimates, and discuss the most compelling challenges and opportunities for the future. Increasingly sophisticated lab experiments have yielded insights into the interaction among heterotrophic respiration, substrate supply, and enzymatic kinetics, and extended incubation‐based analyses across space and time. Observational and manipulative field‐based experiments have used improved measurement approaches to deepen our understanding of the integrated effects of environmental change and disturbance on Rs. Freely‐available observational databases have enabled meta‐analyses and studies probing the magnitude of, and constraints on, the global Rs flux. Key challenges for the field include expanding Rs measurements, experiments, and opportunities to under‐represented communities and ecosystems; reconciling independent estimates of global respiration fluxes and trends; testing and leveraging the power of machine learning and process‐based models, both independently and in conjunction with each other; and continuing the field's tradition of using novel experiments to explore diverse mechanisms and ecosystems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Cystine-knot peptide inhibitors of HTRA1 bind to a cryptic pocket within the active site region

Cystine-knot peptides (CKPs) are naturally occurring peptides that exhibit exceptional chemical and proteolytic stability. We leveraged the CKP carboxypeptidase A1 inhibitor as a scaffold to construct phage-displayed CKP libraries and subsequently screened these collections against HTRA1, a trimeric serine protease implicated in age-related macular degeneration and osteoarthritis. The initial hits were optimized by using affinity maturation strategies to yield highly selective and potent picomolar inhibitors of HTRA1. Crystal structures, coupled with biochemical studies, reveal that the CKPs do not interact in a substrate-like manner but bind to a cryptic pocket at the S1’ site region of HTRA1 and abolish catalysis by stabilizing a non-competent active site conformation. The opening and closing of this cryptic pocket is controlled by the gatekeeper residue V221, and its movement is facilitated by the absence of a constraining disulfide bond that is typically present in trypsin fold serine proteases, thereby explaining the remarkable selectivity of the CKPs. Our findings reveal an intriguing mechanism for modulating the activity of HTRA1, and highlight the utility of CKP-based phage display platforms in uncovering potent and selective inhibitors against challenging therapeutic targets.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Structural complementarity facilitates E7820-mediated degradation of RBM39 by DCAF15

The investigational drugs E7820, indisulam and tasisulam (aryl-sulfonamides) promote the degradation of the splicing factor RBM39 in a proteasome-dependent mechanism. While the activity critically depends on the cullin RING ligase substrate receptor DCAF15, the molecular details remain elusive. Here we present the cryo-EM structure of the DDB1–DCAF15–DDA1 core ligase complex bound to RBM39 and E7820 at a resolution of 4.4 Å, together with crystal structures of engineered subcomplexes. We show that DCAF15 adopts a new fold stabilized by DDA1, and that extensive protein–protein contacts between the ligase and substrate mitigate low affinity interactions between aryl-sulfonamides and DCAF15. Here, our data demonstrate how aryl-sulfonamides neo-functionalize a shallow, non-conserved pocket on DCAF15 to selectively bind and degrade RBM39 and the closely related splicing factor RBM23 without the requirement for a high-affinity ligand, which has broad implications for the de novo discovery of molecular glue degraders.

59 BASIC BIOLOGICAL SCIENCES↗