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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 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Topochemical Deintercalation of Li from Layered LiNiB: toward 2D MBene

The pursuit of two-dimensional (2D) borides, MBenes, has proven to be challenging, not the least because of the lack of a suitable precursor prone to the deintercalation. Here, we studied room-temperature topochemical deintercalation of lithium from the layered polymorphs of the LiNiB compound with a considerable amount of Li stored in between [NiB] layers (33 at. % Li). Deintercalation of Li leads to novel metastable borides (Li~ 0.5 NiB) with unique crystal structures. Partial removal of Li is accomplished by exposing the parent phases to air, water, or dilute HCl under ambient conditions. Scanning transmission electron microscopy and solid-state 7 Li and 11 B NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of Li~ 0.5 NiB and the mechanism of Li-deintercalation. We have shown that the deintercalation of Li proceeds via a “zip-lock” mechanism, leading to the condensation of single [NiB] layers into double or triple layers bound via covalent bonds, resulting in structural fragments with Li[NiB] 2 and Li[NiB] 3 compositions. The crystal structure of Li~ 0.5 NiB is best described as an intergrowth of the ordered single [NiB], double [NiB] 2 , or triple [NiB] 3 layers alternating with single Li layers; this explains its structural complexity. Here, the formation of double or triple [NiB] layers induces a change in the magnetic behavior from temperatureindependent paramagnets in the parent LiNiB compounds to the spin-glassiness in the deintercalated Li~ 0.5 NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).

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

Computational and Experimental Characterization of the Ligand Environment of a Ni-Oxo Catalyst Supported in the Metal–Organic Framework NU-1000

Heterogeneous catalysts exhibit significant changes in composition due to the influence of operating conditions, and these compositional changes can have dramatic effects on catalytic performance. For traditional bulk metal heterogeneous catalysts, relationships between composition and catalytic operating conditions are well documented. However, the influence of operating conditions on the compositions of single-site heterogeneous catalysts remains largely unresolved. To address this, we report a combined computational and experimental characterization of a Ni oxo catalyst under catalytic hydrogenation conditions. Specifically, pair distribution function (PDF) analysis is combined with ab initio thermodynamic modeling to investigate ligand environments present on a Ni oxo cluster supported in the metal–organic framework NU-1000. Comparisons of the experimentally observed and simulated Ni–O coordination numbers and Ni–O, Ni···Ni, and Ni···Zr distances provide insight into the Ni ligand environment under H 2 (g). These comparisons suggest significant OH and H 2 O content and, further, that different Ni ions within the cluster and/or NU-1000 structure may comprise subtly different numbers of these ligands. Further, the observation of significant H 2 O content under H 2 (g) suggests that the NU-1000 support supplies H 2 O to the cluster. Examples of ligand environments that could lead to the observed PDFs are provided. Furthermore, the combination of simulations and experiments provides new insights into the ligand environment for Ni-NU-1000 catalysts that will be useful for understanding the ligand environments of other single-site Ni catalysts as well.

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

Chemical Insights into the Formation of Colloidal Iridium Nanoparticles from In Situ X-ray Total Scattering: Influence of Precursors and Cations on the Reaction Pathway

Iridium nanoparticles are important catalysts for several chemical and energy conversion reactions. Studies of iridium nanoparticles have also been a key for the development of kinetic models of nanomaterial formation. However, compared to other metals such as gold or platinum, knowledge on the nature of prenucleation species and structural insights into the resultant nanoparticles are missing, especially for nanoparticles obtained from Ir$_x$Cl$_y$ precursors investigated here. We use in situ X-ray total scattering (TS) experiments with pair distribution function (PDF) analysis to study a simple, surfactant-free synthesis of colloidal iridium nanoparticles. The reaction is performed in methanol at 50 °C with only a base and an iridium salt as precursor. From different precursor salts–IrCl 3 , IrCl 4 , H 2 IrCl 6 , or Na 2 IrCl 6 –colloidal nanoparticles as small as Ir ~55 are obtained as the final product. The nanoparticles do not show the bulk iridium face-centered cubic ($fcc$) structure but show decahedral and icosahedral structures. The formation route is highly dependent on the precursor salt used. Using IrCl 3 or IrCl 4 , metallic iridium nanoparticles form rapidly from Ir$_x$Cl$_y$$^{n–}$ complexes, whereas using H 2 IrCl 6 or Na 2 IrCl 6 , the iridium nanoparticle formation follows a sudden growth after an induction period and the brief appearance of a crystalline phase. With H 2 IrCl 6 , the formation of different Ir$_n$ ($n$ = 55, 55, 85, and 116) nanoparticles depends on the nature of the cation in the base (LiOH, NaOH, KOH, or CsOH, respectively) and larger particles are obtained with larger cations. As the particles grow, the nanoparticle structure changes from partly icosahedral to decahedral. In conclusion, the results show that the synthesis of iridium nanoparticles from Ir$_x$Cl$_y$ is a valuable iridium nanoparticle model system, which can provide new compositional and structural insights into iridium nanoparticle formation and growth.

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

Atomically Precise Single-Site Catalysts via Exsolution in a Polyoxometalate–Metal–Organic-Framework Architecture

Single-site catalysts (SSCs) achieve a high catalytic performance through atomically dispersed active sites. A challenge facing the development of SSCs is aggregation of active catalytic species. Reducing the loading of these sites to very low levels is a common strategy to mitigate aggregation and sintering; however, this limits the tools that can be used to characterize the SSCs. Here we report a sintering-resistant SSC with high loading that is achieved by incorporating Anderson–Evans polyoxometalate clusters (POMs, MMo 6 O 24 , M = Rh/Pt) within NU-1000, a Zr-based metal–organic framework (MOF). The dual confinement provided by isolating the active site within the POM, then isolating the POMs within the MOF, facilitates the formation of isolated noble metal sites with low coordination numbers via exsolution from the POM during activation. The high loading (up to 3.2 wt %) that can be achieved without sintering allowed the local structure transformation in the POM cluster and the surrounding MOF to be evaluated using in situ X-ray scattering with pair distribution function (PDF) analysis. Notably, the Rh/Pt···Mo distance in the active catalyst is shorter than the M···M bond lengths in the respective bulk metals. Furthermore, models of the active cluster structure were identified based on the PDF data with complementary computation and X-ray absorption spectroscopy analysis.

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

Direct Observation of Circularly Polarized Nonlinear Optical Activities in Chiral Hybrid Lead Halides

Circularly polarized light emission is a crucial application in imaging, sensing, and photonics. However, utilizing low-energy photons to excite materials, as opposed to high-energy light excitation, can facilitate deep-tissue imaging and sensing applications. The challenge lies in finding materials capable of directly generating circularly polarized nonlinear optical effects. In this study, we introduce a chiral hybrid lead halide (CHLH) material system, R/S-DPEDPb 3 Br 8 ·H 2 O (DPED = 1,2-diphenylethylenediammonium), which can directly produce circularly polarized second harmonic generation (CP-SHG) through linearly polarized infrared light excitation, exhibiting a polarization efficiency as high as 37% at room temperature. To understand the spin relaxation mechanisms behind the high polarization efficiency, we utilized two models, so-called D’yakonov–Perel’ (DP) and Bir–Aronov–Pikus (BAP) mechanisms. The unique zigzag inorganic frameworks within the hybrid structure are believed to reduce the dielectric confinement and exciton binding energy, thus enhancing spin polarization, especially in regions with a high excitation pump fluence based on the DP mechanism. In the case of low excitation pump fluence, the BAP mechanism dominates, as evidenced by the observed decrease in the polarization ratio from CP-SHG measurement. Using density functional theory analysis, we elucidate how the distinctive 8-coordination environment of lead bromide building blocks effectively suppresses spin–orbit coupling at the conduction band minimum. This suppression significantly diminishes spin-splitting, thereby slowing the spin relaxation rate.

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

Resolution of Electronic and Structural Factors Underlying Oxygen-Evolving Performance in Amorphous Cobalt Oxide Catalysts

Non-noble-metal, thin-film oxides are widely investigated as promising materials for catalyzing oxygen evolution reactions (OER). Cobalt oxide thin-films that are electrochemically formed in the presence of borate (CoBi) and phosphate (CoPi) serve as important reference catalysts for assessing correlations between oxyhydroxide domain structures with corresponding electronic properties and OER performance. Here, we present a comparison of CoPi and CoBi thin-film catalysts by a combination of advanced X-ray electronic and vibrational spectroscopies of L-edge synchrotron X-ray absorption (XAS), resonant X-ray emission (RXES), resonant inelastic X-ray scattering (RIXS), resonant Raman (RR) scattering, and high-energy X-ray pair distribution function (PDF) analysis. A detailed spectral analysis is presented and identifies relationships between the OER performance and electronic and molecular-type domain structures. XAS shows that CoBi is composed essentially exclusively of cobalt in octahedral coordination, while CoPi contains approximately 17% tetrahedral Co(II), with the remainder in octahedral coordination. Oxygen-mediated 4 p -3 d hybridization through Co-O-Co bonding was detected by RXES and the inter-site dd excitation was observed by RIXS in CoBi, but not in CoPi. RR shows that CoBi resembles a disordered layered LiCoO 2 -like structure while Co- Pi is amorphous. Distinct domain models in the nanometer range for CoBi and CoPi have been proposed on the basis of the PDF analysis coupled to XAS data. In conclusion, the observed differences provide important implications for the enhancement factors in OEC performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Atomic Ordering Enhanced Electrocatalytic Activity of Nanoalloys for Oxygen Reduction Reaction

For oxygen reduction reaction (ORR) over alloy electrocatalysts, the understanding of how the atomic arrangement of the metal species in the nanocatalysts is responsible for the catalytic enhancement is challenging for achieving better design and tailoring of nanoalloy catalysts. This paper reports results of an investigation of the atomic structures and the electrocatalytic activities of ternary and binary nanoalloys, aiming at revealing a fundamental insight into the unique atomic-scale structure-electrocatalytic activity relationship. PtIrCo catalyst and its binary counterparts (PtCo and PtIr) are chosen as a model system for this study. The effect of thermochemical treatment temperature on the atomic-scale structure of the catalysts was examined as a useful probe to the structure-activity correlation. The structural characterization of the binary and ternary nanoalloy catalysts was performed by combining surface sensitive techniques such as XPS and 3D atomic ordering sensitive techniques such as high-energy X-ray diffraction (HE-XRD) coupled to atomic pair distribution function (PDF) analysis (HE-XRD/PDFs) and computer simulations. The results show that the thermal treatment temperature tunes the nanoalloy’s atomic and chemical ordering in a different way depending on the chemical composition, leading to differences in the nanoalloy’s mass and specific activities. A unique structural tunability of the atomic ordering in a platinum-iridium-cobalt nanoalloy has been revealed for enhancing greatly the electrocatalytic activity toward oxygen reduction reaction, which has significant implication for rational design and nanoengineering of advanced catalysts for electrochemical energy conversion and storage.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2014

Bulk Metallic Glass-like Scattering Signal in Small Metallic Nanoparticles

The atomic structure of Ni-Pd nanoparticles has been studied using atomic pair distribution function (PDF) analysis of X-ray total scattering data and with transmission electron microscopy (TEM). Larger nanoparticles have PDFs corresponding to the bulk face-centered cubic packing. However, the smallest nanoparticles have PDFs that strongly resemble those obtained from bulk metallic glasses (BMGs). In fact, by simply scaling the distance axis by the mean metallic radius, the curves may be collapsed onto each other and onto the PDF from a metallic glass sample. In common with a wide range of BMG materials, the intermediate range order may be fit with a damped single-frequency sine wave. When viewed in high-resolution TEM, these nanoparticles exhibit atomic fringes typical of those seen in small metallic clusters with icosahedral or decahedral order. These two seemingly contradictory results are reconciled by calculating the PDFs of models of icosahedra that would be consistent with the fringes seen in TEM. These model PDFs resemble the measured ones when significant atom-position disorder is introduced, drawing together the two diverse fields of metallic nanoparticles and BMGs and supporting the view that BMGs may contain significant icosahedral or decahedral order.

Doan-Nguyen, VVT↗
DOE OSTI2020

Spatial Patterns and Trends of Summertime Low Cloudiness for the Pacific Northwest, 1996–2017

Summertime low clouds are common in the Pacific Northwest (PNW), but spatiotemporal patterns have not been characterized. We show the first maps of low cloudiness for the western PNW and North Pacific Ocean using a 22-year satellite-derived record of monthly mean low cloudiness frequency for May through September and supplemented by airport cloud base height observations. Domain-wide cloudiness peaks in midsummer and is strongest over the Pacific. Empirical orthogonal function (EOF) analysis identified four distinct PNW spatiotemporal modes: oceanic, terrestrial highlands, coastal, and northern coastal. There is a statistically significant trend over the 22-year record toward reduced low cloudiness in the terrestrial highlands mode, with strongest declines in May and June; however, this decline is not matched in the corresponding airport records. The coastal mode is partly constrained from moving inland by topographic relief and migrates southward in late summer, retaining higher late-season low cloud frequency than the other areas.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Proteogenomic characterization of human colon and rectal cancer

We analyzed proteomes of colon and rectal tumors previously characterized by the Cancer Genome Atlas (TCGA) and performed integrated proteogenomic analyses. Protein sequence variants encoded by somatic genomic variations displayed reduced expression compared to protein variants encoded by germline variations. mRNA transcript abundance did not reliably predict protein expression differences between tumors. Proteomics identified five protein expression subtypes, two of which were associated with the TCGA "MSI/CIMP" transcriptional subtype, but had distinct mutation and methylation patterns and associated with different clinical outcomes. Although CNAs showed strong cis- and trans-effects on mRNA expression, relatively few of these extend to the protein level. Thus, proteomics data enabled prioritization of candidate driver genes. Our analyses identified HNF4A, a novel candidate driver gene in tumors with chromosome 20q amplifications. Integrated proteogenomic analysis provides functional context to interpret genomic abnormalities and affords novel insights into cancer biology.

: colorectal cancer, shotgun proteomics, proteogen↗
DOE OSTI2018

99 TcO 4 - remediation by a cationic polymeric network

Direct removal of 99 TcO 4 - from the highly acidic solution of used nuclear fuel is highly beneficial for the recovery of uranium and plutonium and more importantly aids in the elimination of 99 Tc discharge into the environment. However, this task represents a huge challenge given the combined extreme conditions of super acidity, high ionic strength, and strong radiation field. Here in this paper we overcome this challenge using a cationic polymeric network with significant TcO 4 - uptake capabilities in four aspects: the fastest sorption kinetics, the highest sorption capacity, the most promising uptake performance from highly acidic solutions, and excellent radiation-resistance and hydrolytic stability among all anion sorbent materials reported. In addition, this material is fully recyclable for multiple sorption/desorption trials, making it extremely attractive for waste partitioning and emergency remediation. The excellent TcO 4 - uptake capability is elucidated by X-ray absorption spectroscopy, solidstate NMR measurement, and density functional theory analysis on anion coordination and bonding.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Low complexity domains of the nucleocapsid protein of SARS-CoV-2 form amyloid fibrils

The self-assembly of the Nucleocapsid protein (NCAP) of SARS-CoV-2 is crucial for its function. Computational analysis of the amino acid sequence of NCAP reveals low-complexity domains (LCDs) akin to LCDs in other proteins known to self-assemble as phase separation droplets and amyloid fibrils. Previous reports have described NCAP’s propensity to phase-separate. Here we show that the central LCD of NCAP is capable of both, phase separation and amyloid formation. Within this central LCD we identified three adhesive segments and determined the atomic structure of the fibrils formed by each. Those structures guided the design of G12, a peptide that interferes with the self-assembly of NCAP and demonstrates antiviral activity in SARS-CoV-2 infected cells. Our work, therefore, demonstrates the amyloid form of the central LCD of NCAP and suggests that amyloidogenic segments of NCAP could be targeted for drug development.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

The Marginal Ice Zone as a dominant source region of atmospheric mercury during central Arctic summertime

Atmospheric gaseous elemental mercury (GEM) concentrations in the Arctic exhibit a clear summertime maximum, while the origin of this peak is still a matter of debate in the community. Based on summertime observations during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition and a modeling approach, we further investigate the sources of atmospheric Hg in the central Arctic. Simulations with a generalized additive model (GAM) show that long-range transport of anthropogenic and terrestrial Hg from lower latitudes is a minor contribution (~2%), and more than 50% of the explained GEM variability is caused by oceanic evasion. A potential source contribution function (PSCF) analysis further shows that oceanic evasion is not significant throughout the ice-covered central Arctic Ocean but mainly occurs in the Marginal Ice Zone (MIZ) due to the specific environmental conditions in that region. Our results suggest that this regional process could be the leading contributor to the observed summertime GEM maximum. In the context of rapid Arctic warming and the observed increase in width of the MIZ, oceanic Hg evasion may become more significant and strengthen the role of the central Arctic Ocean as a summertime source of atmospheric Hg.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Total X-ray scattering and big-box modeling of pressure-induced local disorder and partial amorphization in CsPbBr 3

The mechanisms governing pressure-induced amorphization and its reversibility in halide perovskites are not yet fully understood, particularly the contribution of local disorder. We performed high-pressure synchrotron total X-ray scattering and reverse Monte Carlo (RMC) big-box modeling using CsPbBr 3 as a model system to investigate short-range structural evolution in both the ordered and partially amorphous phases. While diffraction data indicate that long-range order persists up to 2 GPa, pair distribution function (PDF) analysis reveals significant local distortions, including PbBr 6 octahedral tilting and Cs displacement, which influence the bandgap through a complex interplay between bond compression and angular tilting. Beyond 2 GPa, CsPbBr 3 undergoes partial amorphization, with significant disordering of Cs and Br, while the Pb sublattice remains preserved, allowing for structural recovery upon decompression. Our work, accounting for both short- and long-range structural evolution through RMC modeling, successfully captures how disorder shapes the structural response of halide perovskites under pressure.

critical phenomena↗
DOE OSTI2022

Extracting structural motifs from pair distribution function data of nanostructures using explainable machine learning

Characterization of material structure with X-ray or neutron scattering using e.g. Pair Distribution Function (PDF) analysis most often rely on refining a structure model against an experimental dataset. However, identifying a suitable model is often a bottleneck. Recently, automated approaches have made it possible to test thousands of models for each dataset, but these methods are computationally expensive and analysing the output, i.e. extracting structural information from the resulting fits in a meaningful way, is challenging. Our Machine Learning based Motif Extractor (ML-MotEx) trains an ML algorithm on thousands of fits, and uses SHAP (SHapley Additive exPlanation) values to identify which model features are important for the fit quality. We use the method for 4 different chemical systems, including disordered nanomaterials and clusters. ML-MotEx opens for a type of modelling where each feature in a model is assigned an importance value for the fit quality based on explainable ML.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Autonomous phase mapping of gold nanoparticles synthesis with differentiable models of spectral shape

Autonomous experimentation–or self-driving labs–offers a systematic approach to accelerate materials discovery by integrating automated synthesis, characterization, and data-driven decision-making. We present a closed-loop workflow for the on-demand synthesis and structural characterization of colloidal gold nanoparticles, enabling direct mapping from composition to nanoscale structure. Our framework leverages differentiable models of spectral shape to address two central tasks in self-driving labs: (a) phase mapping, or identifying compositional regions with distinct structural behavior; and (b) material retrosynthesis, or optimizing compositions for target structure. Using functional data analysis, we develop a data-driven model with generative pre-training, active learning, and high-throughput experiments to predict spectral responses across composition space. We demonstrate the approach on seed-mediated growth of gold nanoparticles, showcasing its ability to extract design rules, reveal secondary interactions, and efficiently navigate morphology space. Gradient-based optimization of the models enables inverse design, making this a unified platform.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Giant virus diversity and host interactions through global metagenomics

Our current knowledge about nucleocytoplasmic large DNA viruses (NCLDVs) is largely derived from viral isolates that are co-cultivated with protists and algae. Here we reconstructed 2,074 NCLDV genomes from sampling sites across the globe by building on the rapidly increasing amount of publicly available metagenome data. This led to an 11-fold increase in phylogenetic diversity and a parallel 10-fold expansion in functional diversity. Analysis of 58,023 major capsid proteins from large and giant viruses using metagenomic data revealed the global distribution patterns and cosmopolitan nature of these viruses. The discovered viral genomes encoded a wide range of proteins with putative roles in photosynthesis and diverse substrate transport processes, indicating that host reprogramming is probably a common strategy in the NCLDVs. Furthermore, inferences of horizontal gene transfer connected viral lineages to diverse eukaryotic hosts. We anticipate that the global diversity of NCLDVs that we describe here will establish giant viruses-which are associated with most major eukaryotic lineages-as important players in ecosystems across Earth's biomes.

59 BASIC BIOLOGICAL SCIENCES↗