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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Charge transport in mixed metal halide perovskite semiconductors

Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, in this paper, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm 2 V –1 s -1 . The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Suppression of voltage-decay in Li 2 MnO 3 cathode via reconstruction of layered-spinel coexisting phases

Voltage decay, i.e., the voltage decrease during electrochemical cycling, has been a decade-long challenge for lithium-ion batteries. This issue not only leads to a substantial loss of energy density, but also raises challenges for the battery management system, hindering the commercial application of high capacity lithium-rich oxide. Here, we show that through a combination of electrochemical conditioning and thermal treatment, Li 2 MnO 3 , the parent compound of lithium-rich oxide, which typically displays severe voltage and capacity decay, could be converted into a new phase that essentially suppresses the voltage decay with improved capacity retention and rate performance. Furthermore, by combining atomic-sensitive nuclear magnetic resonance, differential electrochemical mass spectrometry and synchrotron-based resonant inelastic X-ray scattering, we disclose that treatment triggers the formation of three-coexisting phases, i.e., the lithium-rich layered, spinel and defect spinel phases, which enables improved reversibility of the oxygen redox activity and enhanced manganese redox reactions in the initial cycle. Our findings suggest the key role of the local structure in the voltage decay problem and provide insights for material optimizations towards lithium- and manganese-rich cathodes without the voltage decay.

25 ENERGY STORAGE↗
DOE OSTI2022

STEM imaging of irradiation induced defects in Eurofer97 steel variants irradiated in the EUROfusion collaboration

Ten exploratory variants of Eurofer97 reduced activation ferritic martensitic (RAFM) steel were irradiated in HFIR to ~2.94 – 32.4 dpa, 300±30 °C as a part of the EUROfusion collaboration. The irradiations were performed in rabbit capsules. ES21-22 capsule were used for irradiating SS-J3 tensile samples while M4CVN bend bar samples were irradiated in ES31-35 capsules. The mechanical properties and multi-length scale characterization of the microstructures of these ten steels, designated as H, I, P, J, K, L, M, N, O, P and reference E, in the nonirradiated form was reported in "Mechanical properties and microstructure characterization of unirradiated Eurofer-97 steel variants for the EUROfusion project, ORNL/SPR-2018/882," while their irradiated properties and some microstructure analysis was reported in "Post-irradiation examination of Eurofer97 steel variants irradiated to 2.5 dpa, ~300 °C in HFIR for the EUROfusion program, ORNL/SPR-2020/1440." Here, additional microstructures using TEM/STEM and STEM-EDX of the irradiated steels is presented. Characterization was performed at the Low Activation Materials Development and Analysis (LAMDA) laboratory.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Revealing multiple classes of stable quantum emitters in hexagonal boron nitride with correlated optical and electron microscopy

Defects in hexagonal boron nitride (hBN) exhibit high-brightness, room-temperature quantum emission, but their large spectral variability and unknown local structure challenge their technological utility. Here, we directly correlate hBN quantum emission with local strain using a combination of photoluminescence (PL), cathodoluminescence (CL) and nanobeam electron diffraction. Across 40 emitters, we observe zero phonon lines (ZPLs) in PL and CL ranging from 540 to 720 nm. CL mapping reveals that multiple defects and distinct defect species located within an optically diffraction-limited region can each contribute to the observed PL spectra. Local strain maps indicate that strain is not required to activate the emitters and is not solely responsible for the observed ZPL spectral range. Instead, at least four distinct defect classes are responsible for the observed emission range, and all four classes are stable upon both optical and electron illumination. Our findings offer a foundation for future atomic-scale optical characterization of colour centres.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tuning the Placement of Pt “Single Atoms” on a Mixed CeO 2 –TiO 2 Support

Defect sites on the oxide supports can be used to anchor and activate "single-atoms" catalysts (SACs). By engineering the anchoring sites for supporting SACs, one can alter their electronic and atomic structures which, in turn, define their activity, selectivity, and stability for catalytic reactions. To create and tune unique sites for Pt SACs on CeO 2 support, in this work, we synthesized a system consisting of CeO 2 decorated on TiO 2 nano-oxides for supporting the Pt SACs and investigated the effect of Pt weight loading. Here, a combination of multiple structural characterization methods including diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) were employed to characterize the distribution of charge states of single atoms and evaluate the heterogeneity of their binding sites. We have found that the placement of Pt atoms can be tuned on a mixed oxide surface by changing the weight loading of Pt.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Unifying principles for catalytic hydrotreating processes (Final Technical Report)

This project builds on the hypothesis that the hydrotreating processes for the removal of oxygen and sulfur are fundamentally similar at the atomic-scale and existing knowledge from the treatment of petroleum derived feedstock can be leveraged for the design of novel catalysts for the upgrade of bio-oil. We tested this hypothesis by comparing computed potential energy diagrams for hydrodesulfurization (HDS) of thiophene over MoS 2 with hydrodeoxygenation (HDO) of furan over MoO 3 and concluded that certain aspects, such as catalyst promotion with transition metals, are valid strategies for both reactions. On the other hand, we also noticed significant differences in the mechanism for hydrogen (H 2 ) activation, which requires sites with metallic character. While MoS 2 is known to have metallic edge states that can catalyze H 2 dissociation, this elementary step is prohibitively slow on defect-free oxides. Only in the presence of vacancies or by creating metal/oxide interfaces can efficient H 2 activation sites during HDO be formed. The need for bifunctional catalyst when it comes to efficient and selective HDO or dehydrogenation reactions was further corroborated in joint experimental and theoretical studies of the Guerbet reaction for the coupling of biomass derived oxygenates over PdCu alloys, nitrate reduction over In-promoted Pd nanoparticles, and ethylene dehydroaromatization over Ga-exchanged ZSM-5 zeolites. All of these catalytic systems have in common that catalytic sites with distinct functional requirements are needed to create a working catalyst. Detailed computational studies were carried out for HDO of m -cresol and phenol on Ru-modified TiO 2 surfaces, which allowed us to attribute catalytic activity to the metal/oxide interface. A surprising finding was that heterolytic cleavage of the H-H bond across the Ru/TiO 2 interface was critically important, despite lower barriers for homolytic H 2 activation on Ru metal. The explanation lies in the high barriers for hydrogen spillover from Ru to TiO 2 , which becomes unnecessary in the heterolytic activation pathway. Moreover, we also reported that proton transfer steps between metal and oxide sites are mediated by weakly adsorbed surface water. During attempts to develop and validate a kinetic Monte Carlo (kMC) model for HDO reactions at the Ru/TiO 2 interface, it became clear that lateral interactions are paramount to describe realistic surface chemistry and without these interactions, the reduction and hydroxylation behavior from our simulations was inconsistent with reported experiments. To assess the importance of lateral interactions in popular computational catalyst design strategies relying on the identification of reactivity descriptors, which can be used along with Brønsted–Evans–Polanyi (BEP) and scaling relations as input to a microkinetic model (MKM) to make predictions for activity or selectivity trends, we compared predicted trends with those obtained from descriptor-based kMC models. We critically evaluated the benefits of kMC over MKM in terms of trend predictions and computational cost when using only a small set of input parameters. After confirming that in the absence of lateral interactions the kMC and MKM approaches yield identical trends and mechanistic information, we observed substantial differences between the two kinetic models when lateral interactions were introduced. The mean-field implementation applies coverage corrections directly to the descriptors, causing an artificial overprediction of the activity of strongly binding metals. In contrast, the cluster expansion in kMC implementation can differentiate among the highly active metals but it is very sensitive to the set of included interaction parameters. Considering that computational screening relies on a minimal set of descriptors, for which MKM makes reasonable trend predictions at a ca. three orders of magnitude lower computational cost than kMC, we concluded that the MKM approach does provide an overall better entry point for computational catalyst design. Overall, this project has led to 11 peer-reviewed publications, and their scientific is impact is well illustrated by their combined 702 citations.

08 HYDROGEN↗
DOE OSTI2020

Effects of transition metals on the evolution of polymer-derived SiOC ceramics

This work focuses on catalytic graphitization from different metals, iron (Fe), cobalt (Co), and nickel (Ni), for inducing carbon growth in silicon oxycarbides (SiOCs) during the pyrolysis. Fe, Co, and Ni-modified SiOCs were synthesized by pyrolysis to 900, 1100, and 1300 °C respectively in Ar. The transition metals induced the formation of the corresponding metal silicides, β-SiC, and graphitic carbon with the catalytic activity in the order of Fe > Co > Ni, in agreement with the activation energy calculation based on the carbon types and amounts. Lateral growth of turbostratic carbon followed a 2D grain growth process and its point-like defect density decreased based on the catalytic order of the transition metals, with SiOC/Fe having the lowest defect density. Quantitative analysis of the XPS results with Rietveld refinement illustrated that the phase separation of SiOC is more dominant than local carbothermal reduction between SiO 2 and C in the SiOC/M (M = Ni, Co, or Fe) systems. Understanding the catalytic graphitization effect of Ni, Co, and Fe on polymer derived ceramics offers new strategies in increasing high-temperature phase amounts and thus creating novel materials for heterogeneous catalysis, magnetic, and other applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Enhanced and stabilized hydrogen production from methanol by ultrasmall Ni nanoclusters immobilized on defect-rich h-BN nanosheets

Employing liquid organic hydrogen carriers (LOHCs) to transport hydrogen to where it can be utilized relies on methods of efficient chemical dehydrogenation to access this fuel. Therefore, developing effective strategies to optimize the catalytic performance of cheap transition metal-based catalysts in terms of activity and stability for dehydrogenation of LOHCs is a critical challenge. Here, we report the design and synthesis of ultrasmall nickel nanoclusters (∼1.5 nm) deposited on defect-rich boron nitride (BN) nanosheet (Ni/BN) catalysts with higher methanol dehydrogenation activity and selectivity, and greater stability than that of some other transition-metal based catalysts. The interface of the two-dimensional (2D) BN with the metal nanoparticles plays a strong role both in guiding the nucleation and growth of the catalytically active ultrasmall Ni nanoclusters, and further in stabilizing these nanoscale Ni catalysts against poisoning by interactions with the BN substrate. We provide detailed spectroscopy characterizations and density functional theory (DFT) calculations to reveal the origin of the high productivity, high selectivity, and high durability exhibited with the Ni/BN nanocatalyst and elucidate its correlation with nanocluster size and support–nanocluster interactions. This study provides insight into the role that the support material can have both regarding the size control of nanoclusters through immobilization during the nanocluster formation and also during the active catalytic process; this twofold set of insights is significant in advancing the understanding the bottom-up design of high-performance, durable catalytic systems for various catalysis needs.

08 HYDROGEN↗
DOE OSTI2022

Mixed excitonic nature in water-oxidized BiVO 4 surfaces with defects

BiVO 4 is a promising photocatalyst for efficient water oxidation, with surface reactivity determined by the structure of active catalytic sites. Surface oxidation in the presence of oxygen vacancies induces electron localization, suggesting an atomistic route to improve the charge transfer efficiency within the catalytic cycle. In this paper, we study the effect of oxygen vacancies on the electronic and optical properties at BiVO 4 surfaces upon water oxidation. We use density functional theory and many-body perturbation theory to explore the change in the electronic and quasiparticle energy levels and to evaluate the electron-hole coupling as a function of the underlying structure. Further we show that while the presence of defects alters the atomic structure and largely modifies the wave-function nature, leading to defect-localized states at the quasiparticle gap region, the optical excitations remain largely unchanged due to the substantial hybridization of defect and nondefect electron-hole transitions. Our findings suggest that defect-induced surface oxidation supports improved electron transport, both through bound and tunable electronic states and via a mixed nature of the optical transitions, expected to reduce electron-hole defect trapping.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Enhancement of radiation detection performance with reduction of EH 6/7 deep levels in n-type 4H–SiC through thermal oxidation

We report the effect of EH 6/7 electron trap centers alone on the performance of high-resolution radiation detectors fabricated on n-type 4H–SiC epitaxial layers. A Schottky barrier detector (SBD) and a metal-oxide-semiconductor (MOS) capacitor detector fabricated using two sister samples derived from the same 50 μm 4H–SiC parent wafer exhibited widely different energy resolutions of 0.4% and 0.9% for 5486 keV alpha particles. An equivalent noise charge model analysis ruled out the effect of the detector capacitance and the leakage current on the resolution of the detectors. Deep level transient spectroscopic studies revealed the presence of two trapping centers in each detector within the temperature scan range 240–800 K. The Z 1/2 center, a potential electron trap, was detected in both the detectors in equal concentration, which suggested that the observed difference in the energy resolution is due to the presence of the other defect, the EH 6/7 center, in the SBD. The capture cross section of the EH 6/7 center was calculated to be three orders of magnitude higher than the second defect [a carbon antisite vacancy (CAV) center] observed in the MOS detector with an activation energy of 1.10 eV, which accounted for the enhanced electronic trapping in the SBD leading to its poor energy resolution. It has been proposed that the EH 6/7 centers in the SBD have likely been reconfigured to CAV pairs during the thermal growth of the silicon dioxide layer in the MOS detector. The proposed formation mechanism of CAV, a stable qubit state for quantum information processing, addresses the outstanding questions related to the role of defect dynamics in their formation.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2021

Growth–defense trade‐offs and yield loss in plants with engineered cell walls

Summary As a major component of plant secondary cell walls, lignin provides structural integrity and rigidity, and contributes to primary defense by providing a physical barrier to pathogen ingress. Genetic modification of lignin biosynthesis has been adopted to reduce the recalcitrance of lignified cell walls to improve biofuel production, tree pulping properties and forage digestibility. However, lignin‐modification is often, but unpredictably, associated with dwarf phenotypes. Hypotheses suggested to explain this include: collapsed vessels leading to defects in water and solute transport; accumulation of molecule(s) that are inhibitory to plant growth or deficiency of metabolites that are critical for plant growth; activation of defense pathways linked to cell wall integrity sensing. However, there is still no commonly accepted underlying mechanism for the growth defects. Here, we discuss recent data on transcriptional reprogramming in plants with modified lignin content and their corresponding suppressor mutants, and evaluate growth‐defense trade‐offs as a factor underlying the growth phenotypes. New approaches will be necessary to estimate how gross changes in transcriptional reprogramming may quantitatively affect growth. Better understanding of the basis for yield drag following cell wall engineering is important for the biotechnological exploitation of plants as factories for fuels and chemicals.

Ha, Chan Man↗
DOE OSTI2024

Active Nematic Ratchet in Asymmetric Obstacle Arrays

We numerically investigate the effect of an asymmetric periodic obstacle array in a two-dimensional active nematic. We find that activity in conjunction with the asymmetry leads to a ratchet effect or unidirectional flow of the fluid along the asymmetry direction. The directional flow is still present even in the active turbulent phase when the gap between obstacles is sufficiently small. We demonstrate that the dynamics of the topological defects transition from flow-mirroring to smectic-like as the gap between obstacles is made smaller, and explain this transition in terms of the pinning of negative winding number defects between obstacles. This also leads to a non-monotonic ratchet effect magnitude as a function of obstacle size, so that there is an optimal obstacle size for ratcheting at fixed activity.

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

Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS 2

We report the nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS 2 . Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS 2 remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS 2 under reaction conditions (H 2 atmosphere, 100–600 °C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 ± 0.4 S atoms as nearest neighbors (above 400 °C in an H 2 atmosphere). Conversely, the 6-fold Mo–Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS 2 is herein elucidated for applications in optoelectronics and catalysis.

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

Quantifying Large Lattice Relaxations in Photovoltaic Devices

Temporal variations of Cu(In,Ga)Se 2 photovoltaic device properties during light exposure at various temperatures and voltage biases for times up to 100 h are analyzed using the kinetic theory of large lattice relaxations. Open-circuit voltage and p-type doping increased with charge injection and decreased with temperature at low injection conditions. Furthermore, lattice relaxation can account for both trends and activation energies extracted from the data are approximately 0.9 and 1.2 eV for devices with lower and higher sodium content, respectively. In these devices, increased sodium content resulted in higher initial p-type doping with greater stability. First-principles calculations providing revised activation energies for the (V Se -V Cu ) complex suggest that this defect does not account for the metastability observed here.

14 SOLAR ENERGY↗
DOE OSTI2023

Collaborative R&D with First Solar on Understanding Performance Limitations in CdTe (Project 1 "CdTe" - Mods 0-10, 13, 14-A1, 17)

This CRADA involves analyses on a variety of CdTe and CdTe-PV related materials, test structures, and solar cells produced at FSLR or NREL. Single-crystal (sx) material will be primarily MBE grown and provided by FSLR. Joint activities are focused on establishing the appropriate quality metrics as a basis for high performing sx devices and to study the dopability of the material. Polycrystalline (px) materials will be provided by NREL, FSLR, or fabricated jointly. Px activities are focused on the characterization of performance limiting mechanisms including bulk defects, grain boundaries, and the hetero-interface. A combination of growth, characterization, and theory will be applied. Analysis will include techniques that are well established in CdTe research at NREL (e.g., LIV/DIV/CV, AS/DLTS, LTPL, TRPL) as well as techniques that have not been widely applied to the PV part of CdTe technology (e.g., PCD, CL, uPL, SE).

14 SOLAR ENERGY↗
DOE OSTI2022

Effects of penta‐coordinated Al 3+ sites and Ni defective sites on Ni/ Al 2 O 3 for CO methanation

Abstract Engineering sophisticated structure of Al 2 O 3 and controlling the structure of counterpart metal active sites remain challenges to achieve a high catalytic‐performance in heterogeneous catalysis. Herein, we present a confinement strategy to stabilize homogeneous Ni by penta‐coordinated Al 3+ anchoring sites in Al 2 O 3 . This approach is involved in using a metal–organic framework as host to load Ni 2+ ions, by the aim of producing a confined Ni/Al 2 O 3 catalyst after a standard calcination. Metal–support interaction between Ni and Al 2 O 3 was tailored to be medium to avoid the formation of inactive NiAl 2 O 4 , which favors the generation of more available Ni active sites accessible to the reactants. The resultant Ni/Al 2 O 3 exhibited superior catalytic performance in comparison with the control Ni/Al 2 O 3 in CO methanation owing to the presence of defective sites on sufficient Ni 0 surface. Furthermore, the presence of oxygen vacancies on Al 2 O 3 and hydrogen spillover contributed toward excellent coke resistance properties in the reaction.

Engineering↗
DOE OSTI2020

Luminescence Quenching via Deep Defect States: A Recombination Pathway via Oxygen Vacancies in Ce-Doped YAG

Luminescence quenching via nonradiative recombination channels limits the efficiency of optical materials such as phosphors and scintillators and therefore has implications for conversion efficiency and device lifetimes. In materials such as Ce-doped yttrium aluminum garnet (YAG:Ce), quenching shows strong dependence on both temperature and activator concentration, limiting the fabrication of high-intensity white-light emitting diodes with high operating temperatures. Here, we reveal by means of first-principles calculations an efficient recombination mechanism in YAG:Ce that involves oxygen vacancies and gives rise to thermally activated concentration quenching. We demonstrate that the key requirements for this mechanism to be active are localized states with strong electron-phonon coupling. These conditions are commonly found for intrinsic defects such as anion vacancies in wide band gap materials. The present findings are therefore relevant to a broad class of optical materials and shine light on thermal quenching mechanisms in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗