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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Spatially Resolved Mapping of Three-Dimensional Molecular Orientations with ~2 nm Spatial Resolution through Tip-Enhanced Raman Scattering

We record local optical field images of silver nanocubes (75 nm) using tip-enhanced Raman (TER) spectral imaging. The images that we observe are consistent with several recent reports from our group, but here, we demonstrate sub-2 nm spatial resolution in local optical field nanoimaging under ambient laboratory conditions. This is achieved by scanning the substrate (nanocube on Si) relative to a 4-thiobenzonitrile (TBN)-functionalized Ag-coated TER probe. The spatial resolution that we obtain necessitates that only a few molecules govern the recorded optical response; molecular orientation becomes an important consideration in such measurements. We model the orientation through geometry optimization of a TBN molecule chemisorbed onto an Ag79 cluster (sphere with a ~1 nm diameter). Using the computed orientation of the cluster-bound molecule, we then model the optical response using formalism that accounts for the orientation of the molecule relative to vector components of the local optical fields. We find optimal agreement between experiment and theory. In effect, this work reveals the parallels between single-molecule Raman scattering and high-spatial-resolution TER spectroscopy, even when the images themselves cannot be used to visualize a single molecule in real space.

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

Spatio-Spectral Characterization of Multipolar Plasmonic Modes of Au Nanorods via Tip-Enhanced Raman Scattering

Tip-enhanced Raman (TER) spectral images of 4-thiobenzonitrile-coated Au nanorods map the spatial profiles and trace the resonances of dipolar and multipolar plasmonic modes that are characteristic of the imaged particles. For any particular rod, we observe sequential transitions between high-order modes at low frequency shifts and lower-order modes at higher frequencies. We also notice that higher-order modes (up to $m$ = 4) are generally observed for long rods as compared to their shorter analogues, where longitudinal dipolar resonances ($m$ = 1) are observable. In effect, this research adds a new dimension to local optical field mapping via TERS, which we have previously explored. Not only can the magnitudes, vector components, local/nonlocal characters of local optical fields be imaged through molecular TERS, but spatially varying local optical resonances are also direct observables.

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

A Closer Look at Tip-Enhanced Raman Chemical Reaction Nanoimages

Tip-enhanced Raman spectroscopy (TERS) is a powerful technique that enables ultrahigh spatial resolution and ultrasensitive chemical imaging. This technique’s ability to track plasmon-induced/enhanced chemical reactions in real space has gained increasing popularity in recent years. Here, in this study, we expose inherent difficulties associated with assigning TERS signatures that accompany chemical transformations. Namely, distinct selection rules as well as the possibility of multiple physical processes/chemical reaction pathways complicate spectral assignments and necessitate caution in assigning the experimental observables. We illustrate the latter using 4,4'-dimercaptostilbene-functionalized plasmonic silver nanocubes, wherein we identify the TERS signatures of product formation, molecular charging, multipolar Raman scattering, and preferred molecular orientations that all lead to distinct and assignable spectral patterns.

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

Multipolar Raman Scattering vs Interfacial Nanochemistry: Case of 4-Mercaptopyridine on Gold

Caution needs to be exercised in associating changes in plasmon-enhanced Raman spectra with chemical transformations. This is demonstrated through a detailed analysis of tip-enhanced Raman (TER) scattering from 4-mercaptopyridine (MPY) on gold. The substrate used consists of gold nanoplates atop a gold surface featuring heterogeneous grooves, all coated with a monolayer of MPY. The brightest spectra across the substrate exhibit features that can only be recovered by considering the generalized polarizability of oriented MPY molecules. Finally, the complex TER spectra we observe do not mark interfacial chemistry, but rather, multipolar TER scattering driven by local field gradients.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

Compensatory Water Effects Link Yearly Global Land CO2 Sink Changes to Temperature

Large interannual variations in the measured growth rate of atmospheric carbon dioxide (CO2) originate primarily from fluctuations in carbon uptake by land ecosystems13. It remains uncertain, however, to what extent temperature and water availability control the carbon balance of land ecosystems across spatial and temporal scales314. Here we use empirical models based on eddy covariance data15 and process-based models16,17 to investigate the effect of changes in temperature and water availability on gross primary productivity (GPP), terrestrial ecosystem respiration (TER) and net ecosystem exchange (NEE) at local and global scales. We find that water availability is the dominant driver of the local interannual variability in GPP and TER. To a lesser extent this is true also for NEE at the local scale, but when integrated globally, temporal NEE variability is mostly driven by temperature fluctuations. We suggest that this apparent paradox can be explained by two compensatory water effects. Temporal water-driven GPP and TER variations compensate locally, dampening water-driven NEE variability. Spatial water availability anomalies also compensate, leaving a dominant temperature signal in the year-to-year fluctuations of the land carbon sink. These findings help to reconcile seemingly contradictory reports regarding the importance of temperature and water in controlling the interannual variability of the terrestrial carbon balance36,9,11,12,14. Our study indicates that spatial climate covariation drives the global carbon cycle response.

Jung, Martin↗
DOE OSTI2020

SERS and the scientific career of Richard P. Van Duyne (1945–2019)

This article describes the scientific career of our dear friend Richard P. Van Duyne. Rick was the discoverer of surface-enhanced Raman spectroscopy (SERS), and over the period from the mid-1970s until his death in 2019, he served as both the intellectual leader of the field, and the technical genius who pushed the field forward through his numerous inventions and discoveries. Rick's work went through many phases, and even involved a significant period of inactivity that Rick was able to break out of, but especially after 2000, there was a period of incredible creativity that ultimately led to a detailed understanding of what the SERS enhancement factor is all about and also led to fabrication techniques for making optimum SERS substrates such that applications of SERS to a wide variety of real-world problems in sensing became possible. In addition, Rick's SERS work spawned numerous related technologies, including index of refraction sensing based on localized surface plasmon resonance (LSPR) measurements, and the extension of SERS to its tip-enhanced cousin TERS, to electrochemical versions of SERS and TERS, and to ultrafast nonlinear techniques. The practical applications he pursued included diagnostics for diseases such as cancer, hand-held glucose sensing, and SERS studies related to art conservation. Furthermore, Rick's legacy will probably be best known through the numerous students, postdocs, and collaborators that passed through his lab and who are now active researchers in areas related to SERS at universities and industrial labs around the world.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Facile fabrication of 2D material multilayers and vdW heterostructures with multimodal microscopy and AFM characterization

Reliable transfer processes that enable manipulation of two-dimensional (2D) materials, e.g., transition metal dichalcogenides (TMDCs) and MXenes, from one substrate to another has been a necessity for successful device fabrication. Here, with both mechanical exfoliation and chemical vapor deposition (CVD) widely used, a versatile, clean, deterministic, and yet simple transfer technique is highly needed. To address such need, we developed a transfer method that takes advantage of wettability contrast between interfaces without the use of sacrificial layers or chemical processes. More importantly, a setup was developed to carry out this transfer method with high sample selectivity and fine control of the position and orientation of transferred TMDC crystals, a feature required for fabrication of the devices based on vertical 2D heterostructures. Using both exfoliated and CVD grown materials and subsequent atomic force microscopy (AFM), photoluminescence (PL), confocal Raman and tip enhanced Raman spectroscopy (TERS) characterization, we ascertained the quality of interfaces resulting from the transfer process while preserving excellent 2D material integrity. PL and TERS maps revealed nanometer-scale heterogeneities in the interfaces of fabricated heterostructures, which should enable further perfection of the transfer technique. TERS/TEPL information were employed to identify areas suitable for nanodevice fabrication, making the reported transfer and characterization methods ideal for making high quality assembly of 2D heterostructure more accessible, which should facilitate exploration of vertical 2D heterostructures for applications in electronics, batteries, solar cells, and twistronics.

2D material transfer↗
DOE OSTI2020

Power-Dependent Dual Analyte Tip-Enhanced Raman Spectral Imaging

In this work, we explore the information content in tip-enhanced Raman (TER) spectral images of gold nanoplates coated with two distinct molecular reporters: 4-thiobenzonitrile (TBN) and 4-nitrothiophenol (NTP). Using our dual analyte approach, we rigorously demonstrate pixel-limited spatial resolution in Raman nano-images that are otherwise dominated by local optical fields that vary more gently in space. Reproducibility is ensured through power dependent TERS mapping. Power-dependent imaging also (i) directly illustrates that TBN is more robust than NTP at higher laser powers, and (ii) reveals an increase in population of the Stark-tuned nitrile resonances of TBN molecules with increasing incident laser power.

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

Tip-Enhanced Raman Nanospectroscopy of Smooth Spherical Gold Nanoparticles

We record nanoscale-resolved chemical images of thiobenzonitrile (TBN)-functionalized smooth gold nanospheres on silicon via tip-enhanced Raman (TER) nano-spectroscopy. The recorded images trace the nascence of the familiar doughnut-shaped scattering profile of nanoparticles on silicon at its origin (the particle surface), which appears as a horseshoe-shaped scattering pattern under our experimental conditions. The local optical field maps are in agreement with their simulated finite-difference time-domain analogues. Analysis of the recorded spectra with the aid of ab initio molecular dynamics-based Raman spectral simulations further suggests that optical rectification and molecular charging take place throughout the course of atomic force microscopy-based TER nanoscale chemical imaging.

Bhattarai, Ashish↗
DOE OSTI2021

Mapping Molecular Adsorption Configurations with < 5 nm Spatial Resolution through Ambient Tip-Enhanced Raman Imaging

We interrogate para-mercaptobenzoic acid (MBA) molecules chemisorbed onto plasmonic silver nanocubes through tip-enhanced Raman (TER) spectral nano-imaging. Through a detailed examination of the spectra, aided by correlation analysis and density functional theory calculations, we find that MBA chemisorbs onto the plasmonic particles with at least two distinct configurations: S- and CO2-bound. High spatial resolution TER mapping allows us to distinguish between the distinct adsorption geometries with a pixel-limited (< 5 nm) spatial resolution under ambient laboratory conditions.

Gabel, Matthew L.↗
DOE OSTI2023

Probing Local Optical Fields via Ultralow Frequency Raman Scattering from a Corrugated Probe

Here we revisit nanoscale local optical field imaging via tip-enhanced Raman scattering (TERS). Rather than taking advantage of molecular reporters to probe different aspects of the local fields, we show how ultralow frequency Raman (ULF) scattering from the (nano-corrugated) metallic probe itself can be used for the same purpose. The bright ULF-TERS response we record allows non-invasive (tapping mode feedback) local field imaging, enables visualizing the local fields of small (down to 20 nm) isolated plasmonic particles, and can also be exploited to distinguish between Si and SiO2 domains with 5 nm spatial resolution. We describe our approach and its limitations, particularly when it comes to using all-metallic vs molecular reporters.

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

Relative Activities of the β-Ketoacyl-CoA and Acyl-CoA Reductases Influence the Product Profile and Flux in a Reversed β-Oxidation Pathway

The β-oxidation pathway, normally involved in the catabolism of fatty acids, can be functionally made to act as a fermentative, iterative, elongation pathway when driven by the activity of a trans-enoyl-CoA reductase (TER). Here, the terminal acyl-CoA reduction to alcohol can occur on substrates with varied chain lengths, leading to a broad distribution of fermentation products in vivo. Tight control of the average chain length and product profile is desirable, as the chain length greatly influences the molecular properties and the commercial value. Lacking a termination enzyme with a narrow chain length preference, we sought alternative factors that could influence the product profile and pathway flux in the iterative pathway. In this study, we reconstituted the reversed β-oxidation (R-βox) pathway in vitro with a purified tri-functional complex (FadBA) responsible for the thiolase, enoyl-CoA hydratase, and hydroxyacyl-CoA dehydrogenase activities, a TER, and an acyl-CoA reductase. Using this system, we determined the rate-limiting step of the elongation cycle and demonstrated that by controlling the ratio of these three enzymes and the ratio of NADH and NADPH, we can influence the average chain length of the alcohol product profile.

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

Tip-Enhanced Raman Chemical and Chemical Reaction Imaging in H 2 O with Sub-3-nm Spatial Resolution

Reproducible chemical and chemical reaction nano-imaging at solid-liquid interfaces remains challenging, particularly when resolutions on the order of a few nm are sought after. In this work, we demonstrate the latter through liquid tip-enhanced Raman (TER) measurements that target gold nanoplates functionalized with 4-mercaptobenzonitrile (MBN). In addition to chemical imaging and local optical field nano-visualization with high spatial resolution, we observe the signatures of 4-mercaptobenzoic acid, which forms as a result of plasmon-induced hydrolysis of MBN. Evidently, the solvent leads to distinct plasmon-induced/enhanced chemical reaction pathways that have not been documented. Here this work shows that such reactions that take place at solid-liquid interfaces can be tracked with a record sub-3 nm spatial resolution via TER spectral nano-imaging in liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Efficient Self-Sensitized Photochemical CO 2 Reduction Using [Re(bpy 2+ )(CO) 3 (I)] 2+ and [Re(bpy 2+ )(CO) 3 (CH 3 CN)] 3+ Photocatalysts with Pendent Ammonium Cations

Rhenium(I) tricarbonyl complexes fac-[Re(bpy)(CO) 3 (L)]n + are the classical examples of self-sensitized photocatalysts capable of the dual roles of light absorption and catalysis. Here, in this work, a series of dicationic halido or tricationic solvento complexes fac-[Re(bpy 2+ )(CO) 3 X] n+ (PF 6 ) n (where X = Cl - or I - (n = 2), or CH 3 CN (n = 3) and bpy 2+ is bipyridine modified by two -CH 2 -(NMe3) + tetra-alkylammonium cations) have been investigated as self-sensitized and sensitized CO 2 reduction photocatalysts. Four structural isomers differing in the cation position have been tested in N,Nʹ-dimethylacetamide solvent (DMA) using 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole (BIH) as the electron donor, and the position of the cationic pendants has a significant impact on the catalyst turnover number and quantum efficiency (ϕ). Up to 455 self-sensitized turnovers of CO and a high photon efficiency (ϕ CO ) of 22% have been achieved. Time-resolved infrared spectroscopy and theoretical calculations were used to characterize the catalytic cycle including the ligand exchange between one-electron reduced (OER) halido and solvento species as well as the binding of CO 2 to the putative two-electron reduced (TER) species. The CO 2 -reactive TER catalyst was formed by disproportionation or intramolecular electron transfer between two forms of the OER catalyst as indicated by the formation of the fully oxidized catalyst concurrent with CO 2 binding. When [Ru(bpy) 3 ] 2+ was used as a sensitizer, catalyst durability improved, and the selectivity toward formate increased as high as 3.3:1 over CO (total TON = 1370) due to acidification of the reaction, which promotes formation of the hydride intermediate, as BIH was consumed and deprotonated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Tidal decomposition of zonal neutral and ion flows in the earth's upper equatorial thermosphere

Evidence is presented for strong coupling between the diurnal components of zonal neutral winds and ion drifts, suggesting that the relative importance of the E- and F-region dynamos be reevaluated. Measurements of zonal neutral winds in the equatorial region of the earth's thermosphere at an average altitude of about 350 km show that the nighttime zonal winds are very similar to the zonal ion-drifts. That similarity is examined, comparing the corresponding tidal components of the 24 hr variations of these two parameters. The amplitude spectrum of the neutral winds exhibits primary and secondary maxima at the diurnal and ter-diurnal frequencies respectively, while the ion-drift spectrum shows only the diurnal maximum. It is found that the simularity between neutral winds and ion-drifts is strongest in the diurnal mode where the phases differ by less than one half hour, the amplitude of the ion-drift being between 70 percent and 80 percent that of the neutral wind, suggesting a first-order relation between the two quantities. The largest difference is found in the steady component representing superrotation; under similar conditions of solar activity, the ions superrotate with a velocity of about 30 m/s and the neutrals with 10 m/s. For the ions, the steady component, the phase of the semi-diurnal component and the amplitude of the ter-diurnal component appear to be sensitive to solar activity and are responsible for the observed solar cycle variations in the times of eastward-to-westward reversals between 0400 and 0700 LT. The ion-drift diurnal amplitude and phase are relatively insensitive to changes in solar activity.

Herrero, F. A.↗
DOE OSTI2025

Cryogenic Optical and Spin Scanning Probe Station for High-throughput Characterization of Solid-state Quantum Defects

This final technical report provides an overview of the key milestones achieved by Advanced Research Systems (ARS), a DOE SBIR/STTR Grant Recipient. ARS’s main objective was to develop a prototype of the Closed Cycle Cryogenic Quantum Probe Station (Avalanche). Designed for near field spectroscopy (Tip Enhanced Photoluminescence, TEPL and Tip Enhanced Raman Spectroscopy TERS) and far field spectroscopy (micro-Raman, micro-PL) is in the final stage of completion. The critical components have been tested and the final System Test of the AFM is scheduled for August 2025.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Identification of 2,2-dinitropropanol, a Hydrolyzed Product of Aged Eutectic Bis(2,2-dinitropropyl) Acetal – Bis(2,2-dinitropropyl) Formal Mixture

Eutectic bis(2,2-dinitropropyl) acetal - bis(2,2-dinitropropyl) formal mixture, nitroplasticizer (herein called NP) has historically been produced by either the ter Meer or oxidative nitration synthesis process, wherein 2,2-dinitropropanol (DNPOH) is produced as an intermediate step in both processes. Therefore that DNPOH, could be present in NP either as a production or hydrolysis degradation product is worth investigation. Here, we synthesized DNPOH, validated the synthesis using NMR, and identified DNPOH in aged NP using liquid chromatography tandem time of flight – quadrupole mass spectrometry (LC-QTOF). Using these results, for the first time we positively identify that DNPOH is absent from NP after its production, but is present as a degradation product through hydrolysis from a thermo-chemical aging profile of NP. To hydrolyze NP, prerequisite is the presence of both water and acid. Despite the presence of water in NP, DNPOH is only generated in the late stage of the aging process, when acid concentration is sufficiently high. It has been previously shown both theoretically and experimentally that a primary step of NP degradation is HONO elimination followed by decomposition, wherein nitric acid, nitrous acid, and water are produced (NP→NP’+2HONO and 2HONO→NO+NO 2 +H 2 O). It is shown from this reaction series that water slows HONO decomposition and therefore in small quantities, 100 s of ppm, water actually stabilizes NP against hydrolysis by equilibrium and reducing acidity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗