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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Steric Effect and Evolution of Surface Species in the Hydrodeoxygenation of Bio-Oil Model Compounds over Pt/HBEA

The hydrodeoxygenation of various bio-oil model compounds (anisole, m-cresol and guaiacol) over Pt/HBEA and the evolution of surface species is investigated. Depending on the functional group, different surface species are formed when the compounds are adsorbed in the presence of Lewis acid sites. For anisole, the methoxy group is decomposed to form phenate species. The methyl and methoxy group remains intact on m-cresol and guaiacol to form cresolate and methoxy phenate species, respectively. The position of these functional groups have a strong influence in the degree of hydrodeoxygenation due to steric hindrance. Based on operando transmission FTIR spectroscopy, a timeline for the formation of polynuclear aromatics and catalyst deactivation is constructed, which is also dependent on the substituents. The slow deactivation rate and low carbon content on Pt/HBEA is discussed.

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

Understanding the Role of Overpotentials in Lithium Ion Conversion Reactions: Visualizing the Interface

Oxide conversion reactions are known to have substantially higher specific capacities than intercalation materials used in Li-ion batteries, but universally suffer from large overpotentials associated with the formation of interfaces between the resulting nanoscale metal and Li 2 O products. Here we use the interfacial sensitivity of operando X-ray reflectivity to visualize the structural evolution of ultrathin NiO electrodes and their interfaces during conversion. We observe two additional reactions prior to the well-known bulk, three-dimensional conversion occurring at 0.6 V: an accumulation of lithium at the buried metal/oxide interface (at 2.2 V) followed by interfacial lithiation of the buried NiO/Ni interface at the theoretical potential for conversion (at 1.9 V). To understand the mechanisms for bulk and interfacial lithiation, we calculate interfacial energies using density functional theory to build a potential-dependent nucleation model for conversion. These calculations show that the additional space charge layer of lithium is a crucial component for reducing energy barriers for conversion in NiO.

25 ENERGY STORAGE↗
DOE OSTI2025

Operando Contactless EFISH Study of the Rate-Determining Step of Light-Driven Water Oxidation on TiO 2 Photoanodes

For many slow solar-fuel-forming reactions, the accumulation of photogenerated minority carriers on the photoelectrode surface leads to light-induced band edge unpinning, affecting the junction properties by decreasing band bending in the semiconductor space charge layer and increasing the driving force of surface reactions in the electric double layer. In this study, we demonstrate a contactless operando electric field-induced second harmonic generation (EFISH) method for measuring the band bending change (δΔΦ SCR L ) on photoelectrodes upon photoexcitation. For ndoped rutile TiO 2 water oxidation photoanodes at pH 7, δΔΦ SCR L increases at more positive potentials or higher illumination power density until it reaches saturation values. We show that under fast mass transport conditions, δΔΦ SCR L is exclusively attributed to the accumulated charged rate-determining species that can be regarded as temporary surface states, and the relationship between the photocurrent and δΔΦ SCR L can be well modeled by assuming that hole trap states function as the reaction center. Kinetic isotope experiments identify proton-coupled electron transfer as the rate-determining step and suggest a possible chemical nature of the key intermediate. We demonstrate that light-induced band edge unpinning is a beneficial feature under high illumination conditions for oxygen evolution reaction on TiO 2 because it maintains the photon-to-current conversion efficiency by enhancing the surface reaction driving force, shedding light on the actual device application.

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

Atomic resolution coherent x-ray imaging with physics-based phase retrieval

Coherent x-ray imaging and scattering from accelerator based sources such as synchrotrons continue to impact biology, medicine, technology, and materials science. Many synchrotrons around the world are currently undergoing major upgrades to increase their available coherent x-ray flux by approximately two orders of magnitude. The improvement of synchrotrons may enable imaging of materials in operando at the atomic scale which may revolutionize battery and catalysis technologies. Current algorithms used for phase retrieval in coherent x-ray imaging are based on the projection onto sets method. These traditional iterative phase retrieval methods will become more computationally expensive as they push towards atomic resolution and may struggle to converge. Additionally, these methods do not incorporate physical information that may additionally constrain the solution. In this work, we present an algorithm which incorporates molecular dynamics into Bragg coherent diffraction imaging (BCDI). This algorithm, which we call PRAMMol (Phase Retrieval with Atomic Modeling and Molecular Dynamics) combines statistical techniques with molecular dynamics to solve the phase retrieval problem. We present several examples where our algorithm is applied to simulated coherent diffraction from 3D crystals and show convergence to the correct solution at the atomic scale.

47 OTHER INSTRUMENTATION↗
DOE OSTI2016

Spatially uniform resistance switching of low current, high endurance titanium–niobium-oxide memristors

Here we analyzed micrometer-scale titanium-niobium-oxide prototype memristors, which exhibited low write-power (< 3 μW) and energy (< 200 fJ per bit per μm 2 ), low read-power (~nW), and high endurance ( > millions of cycles). To understand their physico-chemical operating mechanisms, we performed in operando synchrotron X-ray transmission nanoscale spectromicroscopy using an ultra-sensitive time-multiplexed technique. We observed only spatially uniform material changes during cell operation, in sharp contrast to the frequently detected formation of a localized conduction channel in transition-metal-oxide memristors. We also associated the response of assigned spectral features distinctly to non-volatile storage (resistance change) and writing of information (application of voltage and Joule heating). Lastly, these results provide critical insights into high-performance memristors that will aid in device design, scaling and predictive circuit-modeling, all of which are essential for the widespread deployment of successful memristor applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

In-operando synchrotron experiments of flash sintering carried out in current rate mode

Here, we report first-time results for in-operando flash sintering synchrotron experiments carried out in current rate mode where the specimen, held at a constant temperature, is fed current that is increased at a constant rate. These experiments are unique because the time dependence of the sintering behavior can be stretched out over a longer period (by changing the current rate) than in voltage-to-current experiments in which sintering occurs in a burst at the onset of the flash. Two results are presented: (i) A comparison of temperatures measured with the platinum standard to those predicted by the black body radiation model leading to estimates of the emissivity as a function of porosity whereby emissivity increases from 0.65 to 0.9 as the sample sinters from its green state to full density, and (ii) measurements of the excess lattice expansion as a function of density as the sample sinters continuously while the current is increased. The present work highlights the promise of current rate experiments to obtain results while the sample sinters gradually from its green density to full density (somewhat akin to conventional sintering) for gaining further insights into the mechanisms of flash sintering.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Understanding Soot Development and Thermal Stratification in Combustion Engines through Hyperspectral Non-linear Optical Diagnostics Development

Progress towards next-generation internal combustion engine technologies is dramatically hindered by the complexity of both simulating and measuring key processes, such as thermal stratification and soot formation, in an operating prototype. In general, spectroscopic methods for in-operando probing become limitingly complex at the high pressures and temperature encountered in such systems, and numerical methods for simulating device performance become computationally expensive due to the turbulent flow field, detailed chemistry, and range of important length-scales involved. This report presents parallel experimental and theoretical advances to conquer these limitations. We report the development of high pressure and high temperature ultrafast coherent anti-Stokes Raman spectroscopy measurements, up to a pressure and temperature regime relevant to engine conditions. This report also presents theoretical results using a stochastic one-dimensional turbulence (ODT) model providing insight into the local thermochemical state and its consequences by resolving the full range of reaction-diffusion scales in a stochastic model.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Advances in in situ/operando techniques for catalysis research: enhancing insights and discoveries

Abstract Catalysis research has witnessed remarkable progress with the advent of in situ and operando techniques. These methods enable the study of catalysts under actual operating conditions, providing unprecedented insights into catalytic mechanisms and dynamic catalyst behavior. This review discusses key in situ techniques and their applications in catalysis research. Advances in in situ electron microscopy allow direct visualization of catalysts at the atomic scale under reaction conditions. In situ spectroscopy techniques like X-ray absorption spectroscopy and nuclear magnetic resonance spectroscopy can track chemical states and reveal transient intermediates. Synchrotron-based techniques offer enhanced capabilities for in situ studies. The integration of in situ methods with machine learning and computational modeling provides a powerful approach to accelerate catalyst optimization. However, challenges remain regarding radiation damage, instrumentation limitations, and data interpretation. Overall, continued development of multi-modal in situ techniques is pivotal for addressing emerging challenges and opportunities in catalysis research and technology.

Chen, Linfeng↗
DOE OSTI2024

Quantitative local state of charge mapping by operando electrochemical fluorescence microscopy in porous electrodes

We introduce operando quantitative electrochemical fluorescence state of charge mapping (QEFSM), a non-invasive technique to study operating electrochemical systems along with a new design of optically transparent microfluidic redox flow cells compatible with the most demanding optical requirements. QEFSM allows quantitative mappings of the concentration of a particular oxidation state of a redox-active species within a porous electrode during its operation. In this study, we used confocal microscopy to map the fluorescence signal of the reduced form of 2,7-anthraquinone disulfonate (AQDS) in a set of multistep-chronoamperometry experiments. Calibrating these images and incorporating an analytical model of quinhydrone heterodimer formation with no free parameters, and accounting for the emission of each species involved, we determined the local molecular concentration and the state of charge (SOC) fields within a commercial porous electrode during operation. With this method, electrochemical conversion and species advection, reaction and diffusion can be monitored at heretofore unprecedented transverse and axial resolution (1 μm and 25 μm, respectively) at frame rates of 0.5 Hz, opening new routes to understanding local electrochemical processes in porous electrodes. Here, we observed pore-scale SOC inhomogeneities appearing when the fraction of electroactive species converted in a single pass through the electrode becomes large.

42 ENGINEERING↗
DOE OSTI2019

Surface-supported cluster catalysis: Ensembles of metastable states run the show

It has recently been demonstrated that the dynamic behaviour of surface-supported nanocluster catalysts in realistic reaction conditions defies conventional models used in catalysis. This opens new doors in catalysis by giving more leverage in catalyst design, but also requires a major revision of the understanding of how dynamic heterogeneous catalytic interfaces operate, as well as of the computational approaches of catalyst modelling, and experimental methods of catalyst characterization. Key aspects of the new paradigm include the collective action of many catalyst states that form a statistical ensemble in reacting conditions, the catalytic activity and selectivity being driven by rare and metastable catalyst states, reaction thermodynamics and kinetics being controlled by different states of the catalyst, broken scaling relationships, non-Arrhenius behaviours, and catalyst dynamic restructuring being an essential part of the reaction mechanism. For computation, this complexity means the departure from the standard DFT calculations of reaction mechanisms on a single catalyst structure. For experiment, it calls for the development of operando characterization tools with the per-site resolution and the ability to find the minority sites that govern the catalytic activity. For catalyst design, the goal becomes the creation of the catalyst state (geometric and electronic) that might not be present in the as-prepared catalyst, but would develop in the reaction conditions and would have the desired activity then. While cluster catalysts are the most dramatic in their dynamic fluxionality, other amorphous interfaces also exhibit some of it, and thus are also subject to similar paradigm revision.

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

Low Threshold Voltages Electrochemically Drive Gold Migration in Halide Perovskite Devices

The constituent ions of halide perovskite materials are mobile in the solid state and known to participate in reduction/oxidation reactions. Yet few parameters related to electrochemical processes occurring within devices have been carefully determined. Here, we characterize such reactions in model MAPbI3 perovskite devices, and we quantify threshold voltages for key reactions. Gold is oxidized and mobilized under nitrogen, in the dark, at the MAPbI3/Au interface at 0.8 V. When this interface is buffered with the organic hole transport material (HTM), 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamino)-9,9'-spirobifluorene, MAPbI3 begins to degrade at 1.2 V; degradation liberates ions that subsequently enable Au migration. Thresholds are insensitive to MAPbI3 thickness or choice of organic HTM or oxide cathode, which suggests that these reactions are driven electrochemically; the electric field across the device is less important. These results have profound implications for understanding in operando degradation pathways of optoelectronic perovskite devices that are varied in terms of interface structures, active material compositions, and ranges of external stressors.

42 ENGINEERING↗
DOE OSTI2021

SISGR: Chemomechanics of Far-From-Equilibrium Interfaces (COFFEI)

Portable, reliable, and deployable devices for energy storage and conversion require fundamental changes in design of solid-state composites comprising ceramics and metals. These materials comprise the electrodes and electrolytes of next-generation solid-oxide fuel cells and all solid-state batteries, forming solid-state functional composites. The advent of solid-state batteries – which replace liquid electrolytes with solid electrolytes capable of lithium ion transport for reliable energy storage in portable batteries – and the increased demand space for all solid-state fuel cells capable of oxygen reduction at intermediate temperatures remain important challenges for improved material stability and decreased system cost. However, little is understood about three fundamental facets of materials that enable such solid-state energy applications. First, how do such materials deform, fracture, or delaminate under operando conditions? Second, how does such mechanical deformation limit or facilitate electronic and ionic transport within and across such material interfaces? Third, how we can predictably design interface-rich composites to engineer both structural and electrochemical stability? This COFFEI Group comprised expertise from Materials Science & Engineering and Nuclear Science & Engineering to integrate unique in situ experiments, simulations, and fabricated interfaces that address these fundamental questions in solid-state interfaces of nanoscale composites that will guide solid-state electrochemistry, transport kinetics, and mechanical deformation for nonstoichiometric materials that enable such applications. In particular, we built on COFFEI’s understanding of chemomechanical coupling among defect concentrations, ionic transport, electron transport, and stored elastic energy that is particularly acute in the far-from-equilibrium conditions typical of energy device applications. By tailoring our focus to solid-state interfaces, we addressed these important issues by (a) developing and applying advanced in situ and ex situ characterization tools to characterize model materials and interfaces synthesized with molecular-level control, under both laboratory-controlled and extreme environments representative of energy device operation; and (b) employing computational modeling and simulation frameworks to predict transport mechanisms, reactivity and stability of these model materials and interfaces under significant chemical strains typical of energy device operation. Recent progress provided insights to additional materials systems and electrochemomechanical fatigue and fracture that were not fully envisioned when the program was initiated. Specifically, in the final three years of COFFEI we pursued two integrated thrusts, with complementary focus. Thrust I focused on failure-resistant electrochemomechanical composites, while Thrust II focused on strain-modulated conductivity and reactivity across interfaces. In contrast to our initial COFFEI focus, these thrusts concentrated wholly on solid-state material interfacial interactions and included greater integration of multiscale visualization including in situ electron microscopy of strained structures/interactions and mesoscale simulations. Successful development of functionally superior and long-lived battery and fuel cell systems and stress adaptable oxides requires a deeper, fundamental understanding of the coupling among the historically important subfields of solid-state electrochemistry, transport kinetics, and mechanical deformation for nonstoichiometric metal oxide electrodes. In this program, the understanding and the application of chemomechanical coupling of defect concentrations, ionic transport, electro-catalytic activity and stored elastic energy, particularly acute in the far-from-equilibrium conditions typical of energy device applications, are being refined and implications for device operation clarified, including for miniaturized solid-state batteries and fuel cells.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Can Li: A Career in Catalysis

Prof. Can Li is distinguished for his seminal achievements in fundamental and applied researches in catalysis, especially in advancing the characterization of catalysts and catalytic reactions related to solar energy conversion and fine chemical synthesis. The scope of his research is wide ranging, and he is leading some of the fields. This account highlights his major scientific achievements in advancing the fundamental sciences of characterizing catalysts and understanding the mechanisms of catalytic reactions by developing in situ spectroscopic techniques (e.g., infrared (IR), ultraviolet (UV), Raman, space- and time-resolved spectroscopies and photoelectric imaging), and applying the obtained knowledge in the rational design and synthesis of catalysts for practical applications in photocatalytic, electrocatalytic and photoelectrocatalytic water splitting and CO 2 reduction, chiral synthesis in nanoreactors and ultradeep desulfurization of fuels, and fine chemical synthesis. In particular, his demonstration of the kiloton scale solar fuel production project will be introduced as a successful model for converting fundamental science into practical and impactful applications to convert CO 2 and water into solar fuels. This account also highlights his services to the catalysis communities and international collaborations for promoting catalysis science worldwide.

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

Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites

The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute-alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in-situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalysts—in which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivity—are particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. Furthermore, the integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Quantitative phase analysis of challenging samples using neutron powder diffraction. Sample #4 from the CPD QPA round robin revisited

Here, quantitative phase analysis (QPA) using neutron powder diffraction more often than not involves non-ambient studies where no sample preparation is possible. The larger samples and penetration of neutrons versus X-rays makes neutron diffraction less susceptible to inhomogeneity and large grain sizes, but most well-characterized QPA standard samples do not have these characteristics. Sample #4 from the International Union of Crystallography Commission on Powder Diffraction QPA round robin was one such sample. Data were collected using the POWGEN time-of-flight (TOF) neutron powder diffractometer and analysed together with historical data from the C2 diffractometer at Chalk River. The presence of magnetic reflections from Fe 3 O 4 (magnetite) in the sample was an additional consideration, and given the frequency at which iron-containing and other magnetic compounds are present during in-operando studies their possible impact on the accuracy of QPA is of interest. Additionally, scattering from thermal diffuse scattering in the high- Q region (<0.6 Å) accessible with TOF data could impact QPA results during least-squares because of the extreme peak overlaps present in this region. Refinement of POWGEN data was largely insensitive to the modification of longer d -spacing reflections by magnetic contributions, but the constant-wavelength data were adversely impacted if the magnetic structure was not included. A robust refinement weighting was found to be effective in reducing quantification errors using the constant-wavelength neutron data both where intensities from magnetic reflections were ignored and included. Results from the TOF data were very sensitive to inadequate modelling of the high- Q (low d -spacing) background using simple polynomials.

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

A Polycrystalline Pd Surface Studied by Two-Dimensional Surface Optical Reflectance during CO Oxidation: Bridging the Materials Gap

Industrial catalysts are complex materials systems operating in harsh environments. The active parts of the catalysts are nanoparticles that expose different facets with different surface orientations at which the catalytic reactions occur. However, these facets are close to impossible to study in detail under industrially relevant operating conditions. Instead, simpler model systems, such as single crystals with a well-defined surface orientation, have been successfully used to study gas–surface interactions such as adsorption and desorption, surface oxidation, and oxidation/reduction reactions. To more closely mimic the many facets exhibited by nanoparticles and thereby close the so-called materials gap, there has also been a recent move toward using polycrystalline surfaces and curved crystals. However, these studies are limited either by the pressure or spatial resolution at realistic pressures or by the number of surfaces studied simultaneously. In this work, we demonstrate the use of reflectance microscopy to study a vast number of catalytically active surfaces simultaneously under realistic and identical reaction conditions. As a proof of concept, we have conducted an operando experiment to study CO oxidation over a Pd polycrystal, where the polycrystalline surface acts as a collection of many single-crystal surfaces. Finally, we visualized the resulting data by plotting the reflectivity as a function of surface orientation. We think the techniques and visualization methods introduced in this work will be key toward bridging the materials gap in catalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Quantification of Sub-Pixel Dynamics in High-Speed Neutron Imaging

The high penetration depth of neutrons through many metals and other common materials makes neutron imaging an attractive method for non-destructively probing the internal structure and dynamics of objects or systems that may not be accessible by conventional means, such as X-ray or optical imaging. While neutron imaging has been demonstrated to achieve a spatial resolution below 10 μm and temporal resolution below 10 μs, the relatively low flux of neutron sources and the limitations of existing neutron detectors have, until now, dictated that these cannot be achieved simultaneously, which substantially restricts the applicability of neutron imaging to many fields of research that could otherwise benefit from its unique capabilities. In this work, we present an attenuation modeling approach to the quantification of sub-pixel dynamics in cyclic ensemble neutron image sequences of an automotive gasoline direct injector at a 5 μs time scale with a spatial noise floor in the order of 5 μm.

47 OTHER INSTRUMENTATION↗