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Kulkarni, Ambarish

Publications and source records attributed to Kulkarni, Ambarish.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

LLNL FY24 Aging and Lifetimes Exit Criteria: Milestone 9134, GC#2, EC#2

Surface chemistry of uranium from gases in the ambient atmosphere of the application environment presents significant challenges due to the high degree of reactivity of the substrate and the ubiquity of these gases in experimental setups. Relatively little is known about the chemical mechanism and reaction rates for the catalytic dissociation of atmospheric gases on solid plutonium or uranium as well as the degradation process to form the metal hydride. Experimental studies and age-aware modeling efforts would greatly benefit from detailed atomistic knowledge of the chemical reactivity in these materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Emerging Atomistic Modeling Methods for Heterogeneous Electrocatalysis

Heterogeneous electrocatalysis lies at the center of various technologies that could help enable a sustainable future. However, its complexity makes it challenging to accurately and efficiently model at an atomic level. Herein, we review emerging atomistic methods to simulate the electrocatalytic interface with special attention devoted to the components/effects that have been challenging to model, such as solvation, electrolyte ions, electrode potential, reaction kinetics, and pH. Additionally, we review relevant computational spectroscopy methods. Then, we showcase several examples of applying these methods to understand and design catalysts relevant to green hydrogen. We also offer experimental views on how to bridge the gap between theory and experiments. Finally, we provide some perspectives on opportunities to advance the field.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A reactive molecular dynamics model for uranium/hydrogen containing systems

Uranium-based materials are valuable assets in the energy, medical, and military industries. However, understanding their sensitivity to hydrogen embrittlement is particularly challenging due to the toxicity of uranium and the computationally expensive nature of quantum-based methods generally required to study such processes. In this regard, we have developed a Chebyshev Interaction Model for Efficient Simulation (ChIMES) that can be employed to compute energies and forces of U and UH3 bulk structures with vacancies and hydrogen interstitials with accuracy similar to that of Density Functional Theory (DFT) while yielding linear scaling and orders of magnitude improvement in computational efficiency. Here, we show that the bulk structural parameters, uranium and hydrogen vacancy formation energies, and diffusion barriers predicted by the ChIMES potential are in strong agreement with the reference DFT data. We then use ChIMES to conduct molecular dynamics simulations of the temperature-dependent diffusion of a hydrogen interstitial and determine the corresponding diffusion activation energy. Our model has particular significance in studies of actinides and other high-Z materials, where there is a strong need for computationally efficient methods to bridge length and time scales between experiments and quantum theory.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Elucidating the Initial Steps in α-Uranium Hydriding Using First-Principles Calculations

Hydrogen embrittlement of uranium, which arises due to the formation of a structurally weak pyrophoric hydride, poses a major safety risk in material applications. Previous experiments have shown that hydriding begins on the top or near the surface (i.e., subsurface) of α-uranium. However, the fundamental molecular-level mechanism of this process remains unknown. Here, in this work, starting from pristine α-U bulk and surfaces, we present a systematic investigation of possible mechanisms for the formation of metal hydride. Specifically, we address this problem by examining the individual steps of hydrogen embrittlement, including surface adsorption, subsurface absorption, and the interlayer diffusion of atomic hydrogen. Furthermore, by examining these processes across different facets, we highlight the importance of both (1) hydrogen monolayer coverage and (2) applied tensile strain on hydriding kinetics. Taken together, by studying previously overlooked phenomena, this study provides foundational insights into the initial steps of this overall complex process. We anticipate that this work will guide near-term future development of multiscale kinetic models for uranium hydriding and subsequently identify potential strategies to mitigate this undesired process.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Near-Surface Imaging of the Multicomponent Gas Phase above a Silver Catalyst during Partial Oxidation of Methanol

Fundamental chemistry in heterogeneous catalysis is increasingly explored using operando techniques in order to address the pressure gap between ultrahigh vacuum studies and practical operating pressures. Because most operando experiments focus on the surface and surface-bound species, there is a knowledge gap of the near-surface gas phase and the fundamental information the properties of this region convey about catalytic mechanisms. In this work, we demonstrate in situ visualization and measurement of gas-phase species and temperature distributions in operando catalysis experiments using complementary near-surface optical and mass spectrometry techniques. The partial oxidation of methanol over a silver catalyst demonstrates the value of these diagnostic techniques at 600 Torr (800 mbar) pressure and temperatures from 150 to 410 °C. Planar laser-induced fluorescence provides two-dimensional images of the formaldehyde product distribution that show the development of the boundary layer above the catalyst under different flow conditions. Raman scattering imaging provides measurements of a wide range of major species, such as methanol, oxygen, nitrogen, formaldehyde, and water vapor. Near-surface molecular beam mass spectrometry enables simultaneous detection of all species using a gas sampling probe. Detection of gas-phase free radicals, such as CH 3 and CH 3 O, and of minor products, such as acetaldehyde, dimethyl ether, and methyl formate, provides insights into catalytic mechanisms of the partial oxidation of methanol. The combination of these techniques provides a detailed picture of the coupling between the gas phase and surface in heterogeneous catalysis and enables parametric studies under different operating conditions, which will enhance our ability to constrain microkinetic models of heterogeneous catalysis.

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

Two-Dimensional Conductive Ni-HAB as a Catalyst for the Electrochemical Oxygen Reduction Reaction

Catalytic systems whose properties can be systematically tuned via changes in synthesis conditions are highly desirable for the next-generation catalyst design and optimization. Herein, we present a two-dimensional (2D) conductive metal–organic framework consisting of M-N 4 units (M = Ni, Cu) and a hexaaminobenzene (HAB) linker as a catalyst for the oxygen reduction reaction. By varying synthetic conditions, we prepared two Ni-HAB catalysts with different crystallinities, resulting in catalytic systems with different electric conductivities, electrochemical activity, and stability. We show that crystallinity has a positive impact on conductivity and demonstrate that this improved crystallinity/conductivity improves the catalytic performance of our model system. Additionally, density functional theory simulations were performed to probe the origin of M-HAB’s catalytic activity, and they suggest that M-HAB’s organic linker acts as the active site with the role of the metal being to modulate the linker sites’ binding strength.

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

Supported Metal Pair-Site Catalysts

Complexes with neighboring metal centers in isolated pairs and their analogues on surfaces are drawing increasing attention as catalysts. These include molecular homogeneous catalysts incorporating various ligands, enzymes, and solids that include pairs of metal atoms mounted on supports. Catalysts in this broad class are active for numerous reactions and offer unexplored opportunities to address challenging reactions, such as oxidation of methane and oxidation of water in artificial photosynthesis. The subject of supported metal pair-site catalysts is in its infancy, facing challenges in (a) precise synthesis, (b) structure determination at the atomic scale, and (c) stabilization in reactive atmospheres. In this Perspective, we summarize key characteristics of molecular and enzymatic catalysts that incorporate neighboring metal centers and build on this foundation to assess the emerging literature of metal pair-site catalysts on various supports. The supported catalysts include those synthesized by anchoring molecular dinuclear precursors to support surfaces and those synthesized by selective formation of dinuclear surface species from mononuclear surface species. Examples of metals in this class are rhodium and iridium, and examples of supports are MgO and Fe 2 O 3 . We summarize characterization of these materials by electron microscopy and spectroscopy, emphasizing atomic-resolution aberration-corrected scanning transmission electron microscopy and spectroscopies that provide atomic-scale structural information and allow characterization of functioning catalysts, especially X-ray absorption spectroscopy. Finally, we list some opportunities for research, including suggestions that might lead to structurally well-defined supported metal pair-sites with new catalytic properties.

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

Improved Oxygen Reduction Reaction Activity of Nanostructured CoS 2 through Electrochemical Tuning

Searching for efficient Pt-free oxygen reduction reaction (ORR) electrocatalysts has been actively pursued among the current electrocatalyst research community. The family of transition-metal chalcogenides, especially cobalt disulfide (CoS 2 ), has been reported as competitive ORR catalysts. In this work, we perform a detailed analysis of the intrinsic activity in terms of onset potentials and selectivity toward hydrogen peroxide of CoS 2 in both acid and alkaline medium. Our detailed characterizations of this system via X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and calculated bulk and surface thermodynamics and ORR mechanism reveal pH-dependent electrochemical evolution of the CoS 2 surfaces. Using XPS results before and after ORR in combination with density functional theory (DFT) calculations for individual surfaces reveals sulfur to oxygen substitution, and partial dissolution occurs in acidic media, while thin cobalt oxide films supported by CoS 2 are formed in alkaline media. The comprehensive DFT calculations of the ORR activities on these systems reveal that sulfur is an unlikely ORR active site, while undercoordinated Co metal site in the CoS 2 is less active than very active undercoordinated Co metal site in the Co oxide film. Using these guiding principles, we then demonstrate that electrochemical lithium (Li) tuning of CoS 2 in organic electrolyte increases its ORR performance in both acid and alkaline medium. Detailed characterizations demonstrate that the grain size of CoS 2 particle is considerably reduced and has a much richer surface oxygen content after electrochemical Li tuning (LiET-CoS 2 ) as the direct consequence of the Li galvanostatic cycling. The general efficacy of this method toward transition-metal chalcogenides (T-M-X) is further demonstrated by enhanced ORR activities of CoS and Ni 3 S 2 in alkaline and neutral medium, respectively. This work opens up an opportunity for probing more advanced T-M-X-based catalysts.

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

Trends in Oxygen Electrocatalysis of 3 d ‐Layered (Oxy)(Hydro)Oxides

Abstract First‐row layered transition metal (oxy)(hydro)oxides (LTMOs) form an important class of earth‐abundant materials. They are well‐known as active alkaline oxygen evolution reaction (OER) catalysts, [1,5] and are also often used as metal‐ion battery anodes [6] or as metal‐air bifunctional electrodes. [7] However, their electrochemical activities, particularly for the oxygen reduction reaction (ORR), across the whole 3d ‐element series remain largely unexplored. In this work, we perform a systematic screening of these catalysts for both OER and ORR using a surface edge‐site model with exposed active sites for metal double hydroxides M(OH) 2 , oxyhydroxides MOOH and oxides MO 2 . We establish OER and ORR activities and scaling relations of the whole series across +2, +3 and +4 oxidation states, and successfully reproduce the experimental activities of a few pure layered (oxy)(hydro)oxides. We predict CoOOH/CoO 2 and NiOOH/NiO 2 as active and stable OER catalysts. We also predict Fe(OH) 2 /FeOOH, Mn(OH) 2 /MnOOH and Co(OH) 2 as active and stable ORR catalysts. This makes Co‐(oxy)(hydro)oxides only bifunctional catalyst in this series. Using linear regression, our results indicate that trends across the 3d ‐series can be obtained from only a few bulk, surface and atomic type descriptors. Particularly, we identify that the number of outer d ‐electrons at the surface‐active site as the most important descriptor of activity.

Zhao, Zhenghang↗