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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assess the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. In conclusion, this new window into the surface chemistry of Pt in alkaline electrolyte brings insight into the nature of the rate limiting step, the extent of H ad/absorption, and its persistence at more anodic potentials.

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

In Situ Probing Potassium-ion Intercalation-induced Amorphization in Crystalline Iron Phosphate Cathode Materials

Na-ion and K-ion batteries are promising alternatives for large-scale energy storage applications due to their abundance and low cost. Intercalation of these large ions could cause irreversible structural deformation and partial to complete amorphization in the crystalline electrodes. The designing of new amorphous electrodes is another route to develop electrodes to store these ions reversibly. Lack of understanding of dynamic changes in the amorphous nanostructures during battery operation is the bottleneck for further developments. Here, we report the utilization of in situ digital image correlation and in-operando X-ray diffraction (XRD) techniques to probe dynamic changes in the amorphous phase of iron phosphate during potassium intercalation. In-operando XRD demonstrates amorphization in the electrode’s nanostructure during the first charge/discharge cycle. Additionally, the ex-situ high-resolution transmission electron microscopy further confirms the amorphization after potassium insertion. In situ strain analysis detects the reversible deformation associated with redox reactions in the amorphous phases. Our approach offers new insights on the mechanisms of ion intercalation in the amorphous nanostructures which are highly potent for development of next-generation batteries.

Ozdogru, Bertan↗
DOE OSTI2018

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3 )Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic species were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.

36 MATERIALS SCIENCE↗
DOE OSTI2017

In Situ Probes of Capture and Decomposition of Chemical Warfare Agent Simulants by Zr-Based Metal Organic Frameworks

Zr-based metal organic frameworks (MOFs) have been recently shown to be among the fastest catalysts of nerve-agent hydrolysis in solution. We report a detailed study of the adsorption and decomposition of a nerve-agent simulant, dimethyl methylphosphonate (DMMP), on UiO-66, UiO-67, MOF-808, and NU-1000 using synchrotron-based X-ray powder diffraction, X-ray absorption, and infrared spectroscopy, which reveals key aspects of the reaction mechanism. The diffraction measurements indicate that all four MOFs adsorb DMMP (introduced at atmospheric pressures through a flow of helium or air) within the pore space. In addition, the combination of X-ray absorption and infrared spectra suggests direct coordination of DMMP to the Zr6 cores of all MOFs, which ultimately leads to decomposition to phosphonate products. These experimental probes into the mechanism of adsorption and decomposition of chemical warfare agent simulants on Zr-based MOFs open new opportunities in rational design of new and superior decontamination materials.

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

Dynamically Disordered Lattice in a Layered Pb-I-SCN Perovskite Thin Film Probed by Two-Dimensional Infrared Spectroscopy

The dynamically flexible lattices in lead-halide perovskites may play important roles in extending carrier recombination lifetime in 3D perovskite solar-cell absorbers and in exciton self-trapping in 2D perovskite white-light phosphors. Here, two-dimensional infrared (2D IR) spectroscopy was applied to study a recently reported Pb-I-SCN layered perovskite. The Pb-ISCN perovskite was spin-coated on a SiO 2 surface as a thin film, with a thickness of ~100 nm, where the S 12 CN – anions were isotopically diluted with the ratio of S 12 CN:S 13 CN=5:95 or 1:99 to avoid vibrational coupling and excitation transfer between adjacent SCN – anions. The minor S 12 CN – component was the principal vibrational probe that reported on the structural evolution through 2D IR spectroscopy. Spectral diffusion was observed with a time constant of 4.1 ± 0.3 ps. Spectral diffusion arises from small structural changes that result in sampling of frequencies within the distribution of frequencies that comprise the inhomogeneously broadened absorption spectrum of the in the Pb-I-SCN layered perovskite. These transitions among discrete local structures are distinct from oscillatory phonon motions of the lattice. To accurately evaluate the structural dynamics through measurement of spectral diffusion, the vibrational coupling between adjacent SCN – anions had to be carefully treated. Although the inorganic layers of typical 2D perovskites are structurally isolated from each other, the 2D IR data demonstrated that the layers of the Pb-I-SCN perovskite are vibrationally coupled. When both S 12 CN – and S 13 CN – were pumped simultaneously, cross-peaks between S 12 CN and S 13 CN vibrations and an oscillating 2D band shape of the S 12 CN – vibration were observed. Both observables demonstrate vibrational coupling between the closest SCN – anions, which reside in different inorganic layers. The thin films and the isotopic dilution produced exceedingly small vibrational echo signal fields; measurements were made possible using the near-Brewster’s angle reflection pump-probe geometry.

14 SOLAR ENERGY↗
DOE OSTI2019

Discovery of a chemical probe for PRDM9

PRDM9 is a PR domain containing protein which trimethylates histone 3 on lysine 4 and 36. Its normal expression is restricted to germ cells and attenuation of its activity results in altered meiotic gene transcription, impairment of double-stranded breaks and pairing between homologous chromosomes. There is growing evidence for a role of aberrant expression of PRDM9 in oncogenesis and genome instability. Here we report the discovery of MRK-740, a potent (IC 50 : 80 ± 16 nM), selective and cell-active PRDM9 inhibitor (Chemical Probe). MRK-740 binds in the substrate-binding pocket, with unusually extensive interactions with the cofactor S-adenosylmethionine (SAM), conferring SAM-dependent substrate-competitive inhibition. In cells, MRK-740 specifically and directly inhibits H3K4 methylation at endogenous PRDM9 target loci, whereas the closely related inactive control compound, MRK-740-NC, does not. The discovery of MRK-740 as a chemical probe for the PRDM subfamily of methyltransferases highlights the potential for exploiting SAM in targeting SAM-dependent methyltransferases.

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

Probing sulphur clusters in a microfluidic electrochemical cell with synchrotron-based photoionization mass spectrometry

We present synchrotron-based mass spectrometry to probe products formed in the lithium sulphide electrolyte. In operando analysis was obtained at two different potentials in a vacuum compatible microfluidic electrochemical cell. Mass spectral observations show that the charged electrolyte formed sulfur clusters under dynamic conditions, demonstrating electrolyte electron shuttling.

sulphur cluster, lithium – sulphur battery electro↗
DOE OSTI2021

Development of the materials analysis and particle probe for Proto-MPEX

The Prototype Material Plasma Exposure eXperiment (Proto-MPEX) is a linear plasma device being used in plasma source research and development (R&D) for the proposed MPEX. Once the R&D is completed, this device can also be used to perform plasma–material interaction studies. To perform these studies, a new materials analysis and particle probe (MAPP) has been constructed. The MAPP’s components are a sample holder and manipulator and a custom vacuum chamber with ports to facilitate surface chemistry diagnostics. The MAPP’s overall design enables rapid sample turnaround and in vacuo surface characterization. The surface analysis vacuum chamber has ports for x-ray photoelectron spectroscopy, thermal desorption spectroscopy, back-scatter ion scattering spectroscopy, forward-scatter ion scattering spectroscopy, and direct recoil spectroscopy. The sample manipulator and holder is a Lesker/UHV Multi-Centre Analytical Stage, which is used to place the samples in the exposure region of the Proto-MPEX or the analysis position in the MAPP vacuum chamber. The sample holder has a heating capability of up to 1200 °C for heated exposure and for desorption studies. In this work, we present the MAPP’s design and the first tungsten sample exposure with ex situ analysis that shows a surface deposition layer on the exposed target, highlighting the need for additional in situ measurements on the Proto-MPEX.

Beers, C. J. (ORCID:0000000150985459)↗
DOE OSTI2021

Ultrafast x-ray pump x-ray probe transient absorption spectroscopy: A computational study and proposed experiment probing core-valence electronic correlations in solvated complexes

Femtosecond X-ray pump X-ray probe experiments are currently possible at free electron lasers such as the linac coherent light source (LCLS), which opens new opportunities for studying solvated transition metal-ligand complexes. In order to make the most effective use of these kinds of experiments, it is necessary to determine which chemical properties an X-ray pump pulse will measure. In this paper, we have combined electron cascade calculations and excited-state time-dependent density functional theory calculations to predict the initial state prepared by an X-ray pump and the subsequent X-ray probe spectra at the Fe K-edge in the solvated model transition metal complex, K 4 Fe II (CN) 6 . We find several key spectral features that report on the ligand-field splitting, solvent-solute interactions, and the 3p and 3d electron interactions. We then show how these features could be measured in an experiment.

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

Visualizing the iron atom exchange front in the Fe(II)-catalyzed recrystallization of goethite by atom probe tomography

The autocatalytic redox interaction between aqueous Fe(II) and Fe(III)-(oxyhydr)oxide minerals such as goethite and hematite leads to rapid recrystallization marked, in principle, by an atom exchange (AE) front, according to bulk iron isotopic tracer studies. However, direct evidence for this AE front has been elusive given the analytical challenges of mass-resolved imaging at the nanoscale on individual crystallites. We report successful isolation and characterization of the AE front in goethite microrods by 3D atom probe tomography (APT). The microrods were reacted with Fe(II) enriched in tracer 57 Fe at conditions consistent with prior bulk studies. APT analyses and 3D reconstructions on cross-sections of the microrods reveal an AE front that is spatially heterogeneous, at times penetrating several nanometers into the lattice, in a manner consistent with defect-accelerated exchange. Evidence for exchange along microstructural domain boundaries was also found, suggesting another important link between exchange extent and initial defect content. The findings provide an unprecedented view into the spatial and temporal characteristics of Fe(II)-catalyzed recrystallization at the atomic scale, and substantiate speculation regarding the role of defects controlling the dynamics of electron transfer and AE interaction at this important redox interface.

Taylor, Sandra D.↗
DOE OSTI2021

Probing the electronic properties of the electrified silicon/water interface by combining simulations and experiments.

Silicon (Si) is broadly used in electrochemical and photoelectrochemical devices, where the capacitive and Faradaic reactions at the Si/water interfaces are critical for signal transduction or noise generation. However, probing the electrified Si/water interface at the microscopic level remains a challenging task. Here we focus on hydrogenated Si surfaces in contact with water, relevant to transient electronics and photoelectrochemical modulation of biological cells and tissues. We show that by carrying out first principles molecular dynamics simulations of the Si(100)/water interface in the presence of an electric field we can realistically correlate the computed flat-band potential and tunneling current images at the interface with experimentally measured capacitive and Faradaic currents. Specifically, we validate our simulations in the presence of bias by performing pulsed chronoamperometry measurements on Si wafers in solution. Consistent with prior experiments, our measurements and simulations indicate the presence of voltage-dependent capacitive currents at the interface. We also find that Faradaic currents are weakly dependent on the applied bias, which we relate to surface defects present in newly prepared samples.

Ye, Zifan↗
DOE OSTI2017

Dark energy two decades after: observables, probes, consistency tests

The discovery of the accelerating universe in the late 1990s was a watershed moment in modern cosmology, as it indicated the presence of a fundamentally new, dominant contribution to the energy budget of the universe. Evidence for dark energy, the new component that causes the acceleration, has since become extremely strong, owing to an impressive variety of increasingly precise measurements of the expansion history and the growth of structure in the universe. Still, one of the central challenges of modern cosmology is to shed light on the physical mechanism behind the accelerating universe. In this review, we briefly summarize the developments that led to the discovery of dark energy. Next, we discuss the parametric descriptions of dark energy and the cosmological tests that allow us to better understand its nature. We then review the cosmological probes of dark energy. For each probe, we briefly discuss the physics behind it and its prospects for measuring dark energy properties. Here, we end with a summary of the current status of dark energy research.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Probing decoupling in dark sectors with the cosmic microwave background

The acoustic peaks in the angular power spectrum of cosmic microwave background (CMB) temperature and polarization anisotropies play an important role as a probe of the nature of new relativistic particles contributing to the radiation density in the early universe, parametrized by Δ N eff . Here, the amplitude and phase of the acoustic oscillations provide information about whether the extra species are free-streaming particles, like neutrinos, or tightly-coupled, like the photons, during eras probed by the CMB. On the other hand, some extensions of the Standard Model produce new relativistic particles that decouple from their own non-gravitational interactions after neutrinos, but prior to photons. We study the signature of new relativistic species that decouple during this intermediate epoch. We argue that the decoupling species will cause a scale-dependent change in the amplitude and phase shift of the acoustic oscillations, different from the usual constant shifts on small scales. For intermediate decoupling times, the phase and amplitude shifts depend not only on Δ N eff but the redshift z dec ,X at which the new species decoupled. For Δ N eff > 0.334, a Stage IV CMB experiment could determine N eff at the percent level and z dec ,X at the ~ 10% level. For smaller values, Δ N eff ~ 0.1, constraints on z dec ,X weaken but remain ~ 20–50% for z dec ,X ~ Script O(10 3 –10 4 ). As an application, we study the contributions to Δ N eff and determine the z dec ,X values for simple implementations of the so-called Nnaturalness model.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

Soft X-Ray Second Harmonic Generation as an Interfacial Probe

Nonlinear optical processes at soft x-ray wavelengths have remained largely unexplored due to the lack of available light sources with the requisite intensity and coherence. Here we report the observation of soft x-ray second harmonic generation near the carbon K edge (~284 eV) in graphite thin films generated by high intensity, coherent soft x-ray pulses at the FERMI free electron laser. Our experimental results and accompanying first-principles theoretical analysis highlight the effect of resonant enhancement above the carbon K edge and show the technique to be interfacially sensitive in a centrosymmetric sample with second harmonic intensity arising primarily from the first atomic layer at the open surface. Here, this technique and the associated theoretical framework demonstrate the ability to selectively probe interfaces, including those that are buried, with elemental specificity, providing a new tool for a range of scientific problems.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2017

Effects of optical dopants and laser wavelength on atom probe tomography analyses of borosilicate glasses

Atom probe tomography (APT) is a novel analytical microscopy method that provides three dimensional elemental mapping with sub-nanometer spatial resolution and has only recently been applied to insulating glass and ceramic samples. In this paper, we have studied the influence of the optical absorption in glass samples on APT characterization by introducing different transition metal optical dopants to a model borosilicate nuclear waste glass (international simple glass). A systematic comparison is presented of the glass optical properties and the resulting APT data quality in terms of compositional accuracy and the mass spectra quality for two APT systems: one with a green laser (532 nm, LEAP 3000X HR) and one with a UV laser (355 nm, LEAP 4000X HR). These data were also compared to the study of a more complex borosilicate glass (SON68). The results show that the analysis data quality such as compositional accuracy and total ions collected, was clearly linked to optical absorption when using a green laser, while for the UV laser optical doping aided in improving data yield but did not have a significant effect on compositional accuracy. Comparisons of data between the LEAP systems suggest that the smaller laser spot size of the LEAP 4000X HR played a more critical role for optimum performance than the optical dopants themselves. The smaller spot size resulted in more accurate composition measurements due to a reduced background level independent of the material’s optical properties.

Environmental Molecular Sciences Laboratory↗