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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Real-space inversion and super-resolution of ultrafast scattering

Ultrafast scattering using x-rays or electrons is an emerging method to obtain structure dynamics at the atomic lengthscales and timescales. However, directly resolving in real-space atomic motions is inherently limited by the finite detector range and the probe energy. So, as a result, the time-resolved signal interpretation is mostly done in reciprocal space and relies on modeling and simulations of specific structures and processes. Here, we introduce a model-free approach to directly resolve scattering signals in real space, surpassing the diffraction limit, using scattering kernels and signal priors that naturally arise from the measurement constraints. We demonstrate the approach on simulated and experimental data, recover multiple atomic motions at sub-angstrom resolutions, and discuss the recovery accuracy and resolution limits versus signal fidelity. The approach offers a robust path to obtain high-resolution real-space information of atomic-scale structure dynamics using current time-resolved x-ray or electron scattering sources.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

A Carborane-Derived Proton-Coupled Electron Transfer Reagent

Reagents capable of concerted proton–electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis. To probe the generality of such an approach a class of C,C'-diaryl-ocarboranes is herein explored as a conceptual substitute for the cobaltocene subunit, with an arylamine linkage still serving as a colocalized Brønsted base suitable for protonation. The featured ocarborane (PhCbPh N ) can be reduced and protonated to generate an N–H bond with a weak effective bond dissociation free energy (BDFE eff ) of 31 kcal/mol, estimated with measured thermodynamic data. This N–H bond is among the lowest measured element–H bonds for analyzed nonmetal compounds. Distinct solid-state crystal structures of the one- and two-electron reduced forms of diaryl-o-carboranes are disclosed to gain insight into their well-behaved redox characteristics. The singly reduced, protonated form of the diaryl-o-carborane can mediate multi-ET/PT reductions of azoarenes, diphenylfumarate, and nitrotoluene. In contrast to the aforementioned cobaltocene system, available mechanistic data disclosed herein support these reactions occurring by a rate-limiting ET step and not a CPET step. A relevant hydrogen evolution reaction (HER) reaction was also studied, with data pointing to a PT/ ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.

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

Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$)

Abstract Initially, vanadium dioxide seems to be an ideal first-order phase transition case study due to its deceptively simple structure and composition, but upon closer inspection there are nuances to the driving mechanism of the metal-insulator transition (MIT) that are still unexplained. In this study, a local structure analysis across a bulk powder tungsten-substitution series is utilized to tease out the nuances of this first-order phase transition. A comparison of the average structure to the local structure using synchrotron x-ray diffraction and total scattering pair-distribution function methods, respectively, is discussed as well as comparison to bright field transmission electron microscopy imaging through a similar temperature-series as the local structure characterization. Extended x-ray absorption fine structure fitting of thin film data across the substitution-series is also presented and compared to bulk. Machine learning technique, non-negative matrix factorization, is applied to analyze the total scattering data. The bulk MIT is probed through magnetic susceptibility as well as differential scanning calorimetry. The findings indicate the local transition temperature ( $$T_c$$ T c ) is less than the average $$T_c$$ T c supporting the Peierls-Mott MIT mechanism, and demonstrate that in bulk powder and thin-films, increasing tungsten-substitution instigates local V-oxidation through the phase pathway VO $$_2\, \rightarrow$$ 2 → V $$_6$$ 6 O $$_{13} \, \rightarrow$$ 13 → V $$_2$$ 2 O $$_5$$ 5 .

Wilson, Catrina E. (ORCID:0000000173397318)↗
DOE OSTI2022

A laser ultrasonics-based approach for rapid screening of high entropy alloys

This project demonstrates a laser ultrasonics-based characterization methodology for rapid metallic materials design and discovery via in situ determination of phases, microstructures and elastic properties with respect to temperature. Ultrasonic waves are strongly affected by material microstructure, and therefore serve as a facile means to probe elastic properties, phase content and their size distributions and volume fractions. In this study, a laser ultrasonic technique is used to systematically study the evolution of properties in a set of interrelated simple binary alloys and high entropy alloys (HEA). Phase transformations and microstructural changes inferred from the ultrasonic signals will be correlated with electron microscopy data and predictions using calculations of phase diagrams (CALPHAD). The non-contact and non-destructive ultrasonic testing approach developed in this study could overcome several limitations associated with current material characterization methods for materials discovery. It is expected that laser ultrasonics-based methodology developed in this work will be utilized to evaluate novel graded composition HEAs currently being developed at the Idaho National Laboratory (INL) using advanced manufacturing methods based on direct energy deposition and spark plasma sintering processes, and contribute to accelerate the discovery of HEAs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Neutrino masses and magnetic moments of electron and muon in the Zee Model

We explore parameter space in the Zee Model to resolve the long-standing tension of the electron and muon anomalous magnetic moment (AMM). The model comprises a second Higgs doublet and a charged singlet at electroweak scale and generates Majorana neutrino masses at one-loop level; the neutral partner of the SU(2) L doublet contributes to the AMM of electron and muon via one loop and two-loop corrections. We propose two minimal flavor structures that can explain these anomalies while fitting the neutrino oscillation data. We find that the neutral Higgs resides in the mass range of roughly 10–300 GeV or 1–30 GeV, depending on the flavor structures. The model is consistent with constraints from colliders, electroweak precision data, and lepton flavor violation. To be comprehensive, we examine the constraints from the electric dipole moment (EDM) and find a region of parameter space that gives a sizable contribution to muon EDM while simultaneously giving corrections to muon AMM. In addition to the light scalar, the two charged scalars with masses as low as 100 GeV can induce nonstandard neutrino interactions ε ee as large as 8%, potentially hinting at new physics. We also investigate the projected capability of future lepton colliders to probe the currently allowed parameter space consistent with both electron and muon AMMs via direct searches in the ℓ + ℓ – → ℓ + ℓ – (H→ℓ + ℓ – )channel.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Measurement of high-mass $t\bar{t}\ell ^{+}\ell ^{-}$ production and lepton flavour universality-inspired effective field theory interpretations at $\sqrt{s}=13$ $\text {T}\text {e}\hspace{-1.00006pt}\text {V}$ with the ATLAS detector

Measurements of $t\bar{t}\ell ^{+}\ell ^{-}$ production in the region of high dilepton invariant mass with effective field theory (EFT) interpretations are presented. They are performed using final states with three isolated leptons (electrons or muons) and are based on $\sqrt{s} = 13$ TeV proton–proton collision data with an integrated luminosity of $140\,\textrm{fb}^{-1}$, recorded from 2015 to 2018 with the ATLAS detector at the Large Hadron Collider. Measurements of the $t\bar{t}\ell ^{+}\ell ^{-}$ signal strength and cross-section upper-limits are performed inclusively in lepton flavour and separately for electrons and muons. The study also aims to probe anomalous four-fermion interactions including to test for possible lepton flavor universality violation. No significant deviations from the Standard Model predictions are observed and the measurements are interpreted through the EFT formalism to provide new constraints on the relevant operators.

Aad, G. [CNRS/IN2P3] (ORCID:0000000266654934)↗
DOE OSTI2022

Microstructural Characterization of the Second High Fluence Baffle-Former Bolt Retrieved from a Westinghouse Two-loop Downflow Type PWR

As one of the pressurized water reactor (PWR) internal components, baffle-former bolts (BFBs) are subjected to significant mechanical stress and neutron irradiation from the reactor core during the plant operation. Over the long operation period, these conditions lead to potential degradation and reduced load-carrying capacity of the bolts. In support of evaluating long-term operational performance of materials used in core internal components, the Oak Ridge National Laboratory (ORNL), through the Department of Energy (DOE), Light Water Reactor Sustainability (LWRS) Program, Materials Research Pathway (MRP) has harvested two high fluence BFBs from a commercial Westinghouse two-loop downflow type PWR. The two bolts of interest, i.e. bolts # 4412 and 4416, were withdrawn from service in 2011 as part of a preventative replacement plan. No identification of cracking or potential damage was found for these bolts during their removal in 2011. However, the bolts required a lower torque for removal from the baffle structure than the original torque specified during installation. Irradiation displacement damage levels in the bolts range from 15 to 41 displacements per atom. The goal of this project is to perform detailed microstructural and mechanical property characterization of BFBs following in-service exposures. The information from these bolts will be integral to the LWRS program initiatives in evaluating end of life microstructure and properties. Furthermore, valuable data will be obtained that can be incorporated into model predictions of long-term irradiation behavior and compared to results obtained in high flux experimental reactor conditions. In this report, we present our latest study in FY22 on microstructural characterizations of the second high fluence baffle-former bolt, i.e., bolt # 4412. Analytical electron microscopy and atom probe tomography characterization were performed. The radiation-induced defects in the material add to the large wealth of knowledge for neutron-induced defects in 304/316 grades of stainless steels, specifically for radiation-induced precipitation after high fluence commercial PWR irradiation. The main findings are summarized as follows: 1) The cavity size was considerably larger in the bolt thread section than in the bolt head, with the bolt thread section having a bimodal distribution of cavities greater than ~6 nm in diameter and less than ~3 nm in diameter. The bolt head only had the small-sized cavities. In addition, there was a denuded zone of large cavities near grain boundaries in the thread section of the bolt. 2) Radiation-induced precipitation in the BFB #4412 was highly complex, with the volume fraction, size, and number density of Ni/Si and Cu-rich precipitates depending strongly on the radiation temperature/dose. In many cases, co-precipitates of adjoined clusters were found with Ni/Si-rich precipitates sandwiched between Cu-rich clusters and Mo/Cr/P-rich clusters. 3) Solute segregation out of solution was highest for most solutes in the thread section of the bolt #4412 with the exception of Cu, which experienced more separation out of solution into Curich clusters in the bolt head section. This highlights the difference in the mechanisms for precipitation of Ni/Si clusters, which have the Ni 3 Si phase composition, and precipitation of Cu-rich clusters. 4) There appear to be multiple simultaneous influences that affect the microstructural variation along the length of the bolt that overcomes the ~2X difference in irradiation dose between the bolt head and the bolt thread. The irradiation temperature, thermal/fast neutron ratio variation, potential strain gradient, and exposure to PWR coolant water that each section of the bolt sees may have more influence on the microstructural evolution than the total irradiation dose. The bolt thread and shank, with higher temperature, higher relative fast neutron flux, higher strain, and exposure to coolant but lower dose, underwent more enhanced cavity formation, precipitation, and solute segregation than the bolt head section.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2022

Measurement of the Deeply Virtual Compton Scattering Cross Section from the Proton at 10.6 GeV using the CLAS12 Detector

Deeply Virtual Compton Scattering (DVCS) is an exclusive process that produces a real photon when a lepton scatters from a quark inside a nucleon or a nucleus. Measurement of the DVCS cross section enables the study of the Generalized Parton Distributions (GPD), which plays a central role in understanding the QCD dynamics inside a hadron. Thus, the quark and gluon origin of the nucleon spin and mass can be probed and three-dimensional images of the target nucleon or nucleus can be realized. This thesis presents a cross section analysis of DVCS from the proton in the presence of its background, Bethe-Heitler (BH) process. The CEBAF Large Acceptance Spectrometer for operation at 12 GeV beam energy (CLAS12) collaboration has taken electron-proton scattering data in fall 2018 using a liquid hydrogen target and the 10.6 GeV polarized electron beam from the Continuous Electron Beam Accelerator Facility (CEBAF). The CLAS12 detector is a nearly hermetic fixed-target detector, located in Hall B, Jefferson Lab at Newport News, Virginia. The experimentally determined BH-DVCS cross section is in good agreement with a phenomenological-model based theoretical prediction. The kinematic dependence of the cross section is reported over a wide range. The short-term plan to utilize the results presented here for a thorough tomography study and the long-term plan for GPD studies at future facilities such as the Electron-Ion Collider (EIC) are discussed.

Lee, Sangbaek↗
DOE OSTI2022

A laser ultrasonics-based approach for rapid screening of high entropy alloys

The primary objective of this seed project is to develop a laser ultrasonics-based characterization methodology for rapid metallic materials design and discovery via in situ determination of phases, microstructures and elastic properties with respect to temperature. Ultrasonic waves are strongly affected by material microstructure, and therefore, serve as a facile means to probe elastic properties, phase content and their size distributions and volume fractions. In this study, a laser ultrasonic technique will be used to systematically study the evolution of properties in a set of interrelated simple binary alloys and high entropy alloys (HEA). Phase transformations and microstructural changes inferred from the ultrasonic signals will be correlated with electron microscopy data and predictions using calculations of phase diagrams (CALPHAD). The non-contact and non-destructive ultrasonic testing approach developed in this study could overcome several limitations associated with current material characterization methods for materials discovery. It is expected that the products of the proposed work will be utilized to evaluate novel graded composition HEAs currently being developed at the Idaho National Laboratory (INL) using advanced manufacturing methods based on direct energy deposition and spark plasma sintering processes, and contribute to accelerate the discovery of HEAs.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Visualizing Charge Transport and Nanoscale Electrochemistry by Hyperspectral Kelvin Probe Force Microscopy

Charge-transport and electrochemical processes are heavily influenced by the local microstructure. Kelvin probe force microscopy (KPFM) is a widely used technique to map electrochemical potentials at the nanometer scale; however, it offers little information on local charge dynamics. In this study, we implement a hyperspectral KPFM approach for spatially mapping bias-dependent charge dynamics in timescales ranging from the sub-millisecond to the second regime. As a proof of principle, we investigate the role mobile surface charges play in a three-unit-cell LaAlO 3 /SrTiO 3 oxide heterostructure. We explore machine learning approaches to assist with visualization, pattern recognition, and interpretation of the information-rich data sets. Linear unmixing methods reveal hidden bias-dependent interfacial processes, most likely water splitting, which are essentially unnoticed by functional fitting of the dynamic response alone. Hyperspectral KPFM will be beneficial for investigating nanoscale charge transport and local reactivity in systems involving a possible combination of electronic, ionic, and electrochemical phenomena.

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

Measurement and analysis of the Doppler broadened energy spectra of gamma radiation originating from the annihilation of positrons incident on clean and adsorbate-covered surfaces

We present measurements and theoretical modeling demonstrating the capability of coincidence Doppler broadened (CDB) annihilation gamma spectroscopy to provide element-specific information from the topmost atomic layer of surfaces. Our measurements show that the energy spectra of Doppler-shifted annihilation gamma photons emitted following the annihilation of positrons from the topmost atomic layers of clean and adsorbate covered surfaces of gold (Au), silver (Ag) and copper (Cu) differ significantly. The shape of the Doppler-broadened gamma spectrum, as analyzed using ratio curves, indicates that the elemental composition of the surface can still be identified despite contributions from positronium annihilation and a significant reduction in core electron annihilation. We estimate the chemical composition of the various probed surfaces by modeling the ratios of the measured Doppler spectra with respect to the Doppler spectra from a clean Cu surface using a linear combination of calculated ratio curves. The fitting of the experimental ratio curves was used to obtain an estimate of the elemental composition of Cu surfaces with sulfur segregation, oxygen adsorption, a thin film of Selenium (Se), and a single layer of graphene (SLG). A similar analysis was performed on the Ag surface with environmental adsorbates, the same surface after argon ion sputtering, as well as a sputter cleaned Au surface. The surface compositions obtained from the analysis of the CDB data were compared to the compositions obtained using positron annihilation induced Auger electron spectroscopy (PAES). Our results show that CDB can detect, identify, and quantify, sub-monolayer adsorbates and a single atomic layer deposited on metal substrates.

Lotfimarangloo, Sima [Univ. of Texas, Arlington, T↗
DOE OSTI2022

Automated Experiment in 4D-STEM: Exploring Emergent Physics and Structural Behaviors

Automated experiments in 4D scanning transmission electron microscopy (STEM) are implemented for rapid discovery of local structures, symmetry-breaking distortions, and internal electric and magnetic fields in complex materials. Deep kernel learning enables active learning of the relationship between local structure and 4D-STEM-based descriptors. With this, efficient and “intelligent” probing of dissimilar structural elements to discover desired physical functionality is made possible. This approach allows effective navigation of the sample in an automated fashion guided by either a predetermined physical phenomenon, such as strongest electric field magnitude, or in an exploratory fashion. Therefore, we verify the approach first on preacquired 4D-STEM data and further implement it experimentally on an operational STEM. The experimental discovery workflow is demonstrated using graphene and subsequently extended toward a lesser-known layered 2D van der Waals material, MnPS 3 . This approach establishes a pathway for physics-driven automated 4D-STEM experiments that enable probing the physics of strongly correlated systems and quantum materials and devices, as well as exploration of beam-sensitive materials.

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

Quasi-Two-Dimensional Antiferromagnetic Spin Fluctuations in the Spin-Triplet Superconductor Candidate CeRh 2 As 2

The tetragonal heavy-fermion superconductor CeRh 2 ⁢As 2 (T c = 0.3 K) exhibits an exceptionally high critical field of 14 T for B ∥ c. It undergoes a field-driven first-order phase transition between superconducting states, potentially transitioning from spin-singlet to spin-triplet superconductivity. To further understand these superconducting states and the role of magnetism, we probe spin fluctuations in CeRh 2 ⁢As 2 using neutron scattering. Here, we find dynamic (π, π) antiferromagnetic (AFM) spin correlations with an anisotropic quasi-two-dimensional correlation volume. Our data place an upper limit of 0.31 μ B on the staggered magnetization of corresponding Néel orders at T = 0.08 K. Density functional theory calculations, treating Ce 4⁢ƒ electrons as core states, show that the AFM wave vector connects significant areas of the Fermi surface. Our findings indicate that the dominant excitations in CeRh 2 ⁢As 2 for ℏω⁢ < 1.2 meV are magnetic and suggest that superconductivity in CeRh 2⁢ As 2 is mediated by AFM spin fluctuations associated with a proximate quantum critical point.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Open Source Visualization and Analysis Platform for 3D Reconstructions of Materials by Transmission Electron Microscopy

Three-dimensional characterization of materials at the nano- and meso-scale has become possible with transmission and scanning transmission electron microscopes (S/TEM). Its importance has extended to a wide class of nanomaterials such as hydrogen fuel cells, solar cells, industrial catalysts, new battery materials and semiconductor devices, as well as spanning high-tech industry, universities, and national labs. While capable instrumentation is abundant, this rapidly expanding demand for high-resolution tomography is bottlenecked by software that is instead tailored for lower-dose, biological applications and not optimized for higher-resolution materials applications. Existing tomography fails to utilize the chemical information provided by S/TEM spectrometers. To address this problem, this project delivered a scalable, fully functional, freely-distributable, open Source materials tomography package with a modern user interface that enables automated acquisition, alignment, and real-time reconstruction of raw tomography data, and provides advanced segmentation, three-dimensional chemical visualization and analysis optimized for materials applications. It has established an extendable framework capable of automation for high-throughput for the tomography of materials from data acquisition to visualization. Phase I and II delivered a full-featured, cross-platform, clean and integrated application for S/TEM materials tomography. It can read projection data from the microscope, with graphical tools for alignment of data, tomographic reconstruction, segmentation, and visualization of the reconstructed 3D volume. The entire pipeline can be saved to an XML state file, enabling fully reproducible data processing and analysis with a full Python environment for the development of custom algorithms, processing, and analysis requirements. Phase IIB extended the application to provide real-time tomographic reconstruction, "live updates" as data is processed, analysis of big data, and multi-channel tomography. Here, quantitative assessment of nanomaterials can occur as data is being recorded on a 3D visualization platform that accommodates additional information from multiple channels. We provide unmatched high-throughput tomography, where the complete tomographic pipeline from measurement to 3D visualization can occur rapidly. The project was extended to offer capabilities for micro-CT, X-ray, neutron, focused ion beam, atomic electron tomography and atom probe tomography. With over 600 transmission electron microscopes worldwide and approximately 50 coming online each year, the demand and impact of an open-source tomography tool is large. Significant opportunities exist in high-tech industry, universities, and national labs to enable or enhance three-dimensional imaging at the nanoscale and bring automated high-throughput approaches that will accelerate progress in materials characterization and metrology. The project supports a service based business model by enabling lab-specific acquisition and processing customization and integration-support and development that will be provided into Phase III and beyond.

36 MATERIALS SCIENCE↗
DOE OSTI2021

IMS Rapid Response FY21 Summary Report for: Integrating Patterned Probes with Four-Dimensional Scanning Transmission Electron Microscopy for Unrivaled Crystallographic Structure Determination in Nanomaterials

The initial goal of our 4-dimensional scanning transmission electron microscopy (4D-STEM)-based project was to develop strain resolution two orders of magnitude better than what is now currently possible with electron-based scattering techniques, all while collecting scattering information from 7 different tilt axes at one time [multi-beam electron diffraction (MBED)1 ] through the development of a new electron probe-forming aperture with non-circular features (patterned probes 2 ). We set out to accomplish this through a collaboration with Drs. Colin Ophus and Ben Savitsky at Lawrence Berkeley Laboratory (they are the world-leading experts in developing the complex computational codes required to perform orientation analysis and quantitative strain mapping on our 4D-STEM data sets. We are motivated to invest in this area as it will be the only technique sensitive enough to perform three- dimensional automated crystallographic orientation mapping (ACOM) and strain mapping for materials exposed to external stimulus (a focus of our larger efforts).

36 MATERIALS SCIENCE↗
DOE OSTI2024

Elucidating Photoinduced Processes of Photosystem I Via Multidimensional Electronic and Vibrational Spectroscopies

This project was motivated by an overarching goal to elucidate the mechanism of energy and electron transfer that governs the efficient charge separation in photosystem I (PSI) complexes. PSI is a natural light harvesting complex that drives oxygenic photosynthesis in plants, algae, and cyanobacteria. It uses ~300 tightly packed chlorophylls (Chls) to absorb photons, transfer the excitation energy to the reaction center (RC), and generate a charge separated state with near unity quantum efficiency (QE). A better understanding of the mechanism of energy transfer and charge separation in PSI is required for understanding the high QE of natural light harvesting complexes, and it could lead to the further development of artificial photosynthetic systems for solar energy conversion and modification of light harvesting complexes to improve crop yields. We applied two-dimensional optical spectroscopies to different cyanobacterial photosystem I complexes, including PSI complexes that contain Chl f molecules, to map energy transfer pathways and gain insight into the efficient light harvesting of PSI. We used two-dimensional electronic spectroscopies (2DES) to map energy transfer in Chl a and Chl f containing PSI complexes. To investigate the Chl f PSI complexes, we modified our spectrometer to probe the lower energy states associated with Chl f molecules. We interpreted the 2DES spectra through global analysis procedures to generate maps of energy transfer. We also constructed a two-dimensional electronic vibrational (2DEV) spectrometer that will be used to investigate charge transfer transitions and dynamics within PSI complexes. Measurements were performed on model systems to establish general data analysis procedures for interpreting 2D spectra and gain insight into protein cofactor interactions.

14 SOLAR ENERGY↗
DOE OSTI2023

Probing individual single atom electrocatalyst sites by advanced analytical scanning transmission electron microscopy

Single atom electrocatalysts (SAEs) are promising next-generation materials for promoting a variety of important reactions, such as the oxygen reduction, nitrogen reduction, and CO 2 reduction reactions. While bulk characterization techniques such as X-ray absorption spectroscopy and Mössbauer spectroscopy have significantly enhanced our understanding of these catalysts, direct probing of individual single metal atom sites at the atomic scale is necessary to understand local variations in the properties of these sites and accelerate design and synthesis of improved SAEs. Aberration-corrected scanning transmission electron microscopy (STEM) has become a powerful tool for providing this type of atomic-scale information about SAE metal sites. These sites are typically unstable under the electron beam, however, which, in combination with conventional acquisition methods and detectors, has limited the type and quantity of information obtainable by spectroscopic STEM techniques. Here, we map multiple individual SAE metal sites in a nitrogen-doped carbon containing atomically dispersed Fe and Re (FeReNC) at the atomic scale by direct electron detection electron energy-loss spectroscopy (EELS). Direct electron detection provides an improved signal-to-noise ratio over conventional scintillator-based detectors and enables detection and real space localization of weak signals. In addition, we demonstrate an automated method for identification of metal atom positions, placement of the probe on these sites, and simultaneous EELS and energy dispersive X-ray spectroscopic (EDS) signal acquisition. This simultaneous acquisition of EELS and EDS provides access to the composition and bonding of a wide range of SAE metal sites. In this study, focusing the probe directly on the metal sites also increases the relevant data acquisition rate by more than an order of magnitude over two-dimensional mapping, enabling improved statistical measurements of site properties. The versatility, sensitivity, and speed that these techniques provide enhances our ability to probe the local elemental and chemical environment of a large number of individual SAE metal site structures at the atomic scale, enabling an improved understanding of the variations in the local properties of these electrocatalysts to be gained. As a result, significantly increased information about individual metal sites will be available to future electrochemical studies through these techniques, accelerating the development of advanced SAEs.

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

Solvent Mediated Excited State Proton Transfer in Indigo Carmine

Excited state proton transfer (ESPT) is thought to be responsible for the photostability of biological molecules, including DNA and proteins, and natural dyes such as indigo. However, the mechanistic role of the solvent interaction in driving ESPT is not well understood. Here, the electronic excited state deactivation dynamics of indigo carmine (InC) is mapped by visible pump-infrared probe and two-dimensional electronic-vibrational (2DEV) spectroscopy and complemented by electronic structure calculations. The observed dynamics reveal notable differences between InC in a protic solvent, D$_2$O , and an aprotic solvent, deuterated dimethyl sulfoxide (dDMSO). Notably, an acceleration in the excited state decay is observed in D$_2$O (<10 ps) compared to dDMSO (130 ps). Our data reveals clear evidence for ESPT in D$_2$O accompanied by a significant change in dipole moment, which is found not to occur in dDMSO. We conclude that the ability of protic solvents to form intermolecular H-bonds with InC enables ESPT, which facilitates a rapid nonradiative S$_1$ → S$_0$ transition via the monoenol intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗