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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Electro-chemo-mechanically Driven Ni Exsolution from (Pr,Ce,Ni)O 2−δ : Controlled Nucleation Density and Enhanced Electrode Kinetics

In situ exsolution of metal nanoparticles is a promising strategy to prepare electrocatalysts with enhanced activity and resistance to agglomeration for efficient chemical transformations and energy conversion. Achieving a high nucleation density of nanoparticles under mild conditions and understanding how to tailor the process is important for performance of these electrodes in electrochemical cells. In this work, we demonstrate facile exsolution of Ni nanoparticles using fluorite-structured (Pr,Ce)O 2−δ as the support oxide, driven by electrochemical potential and aided by the metastability of Ni in the solid solution (elastic driving force). We prepare single-phase oriented thin films of (Pr,Ce,Ni)O 2−δ (NPCO) on (Zr,Y)O 2−δ (YSZ) substrates by pulsed laser deposition. With the aid of a high-throughput electrochemical cell that provides a lateral gradient in Nernst voltage, we apply in situ near-ambient pressure synchrotron X-ray photoelectron spectroscopy and ex situ atomic force microscopy to investigate the impact of electrochemical potential on Ni nucleation density. We find that metallic Ni can be successfully exsolved at 550 °C upon cathodic biasing in 20 mTorr O 2 , and its nucleation density increases with increasing electrochemical driving force/decreasing oxygen chemical potential. We further evaluate the electrochemical performance under highly reducing (fuel electrode) conditions by electrochemical impedance spectroscopy. With the exsolved Ni nanoparticles, the surface exchange coefficient of the NPCO is found to be ∼4× higher than for PCO without exsolution. This work confirms mixed conducting fluorites as beneficial host lattices for facile transition-metal exsolution and suggests the possibility for constructing an all ceria-based electrochemical cell with PCO serving as both the cathode and the anode.

36 MATERIALS SCIENCE↗
DOE OSTI2021

On the Origin of Sinter‐Resistance and Catalyst Accessibility in Raspberry‐Colloid‐Templated Catalyst Design

Abstract Nanoparticle (NP) sintering is a major cause of the deactivation of supported catalysts. Raspberry‐colloid‐templated (RCT) catalysts are an emerging class of materials that show an unprecedented level of sinter‐resistance and exhibit high catalytic activity. Here a comprehensive study of the origin of NP stability and accessibility in RCT catalysts using theoretical modeling, 3D electron microscopy, and epitaxial overgrowth is reported. The approach is showcased for silica‐based RCT catalysts containing dilute Pd‐in‐Au NPs previously used in hydrogenation and oxidation catalysis. Modeling of the contact line of the silica precursor infiltrating into the assembled raspberry colloids suggests that a large part of the particles must be embedded into silica, which is confirmed by quantitative visualization of >200 individual NPs by dual‐axis electron tomography. The RCT catalysts have a unique structure in which all NPs reside at the pore wall but have >50% of their surface embedded in the matrix, giving rise to the strongly enhanced thermal and mechanical stability. Importantly, epitaxial overgrowth of Ag on the supported NPs reveals that not only the NP surface exposed to the pore but the embedded interface as well remained chemically accessible. This mechanistic understanding provides valuable guidance in the design of stable catalytic materials.

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

Progresses and Perspectives of All‐Iron Aqueous Redox Flow Batteries

Abstract Redox flow batteries (RFBs) are a promising option for long‐duration energy storage (LDES) due to their stability, scalability, and potential reversibility. However, solid‐state and non‐aqueous flow batteries have low safety and low conductivity, while aqueous systems using vanadium and zinc are expensive and have low power and energy densities, limiting their industrial application. An approach to lower capital cost and improve scalability is to utilize cheap Earth‐abundant metals such as iron (Fe). Nevertheless, all‐iron RFBs have many complications, involving voltage loss from ohmic resistance, side reactions such as hydrogen evolution, oxidation, and most significantly electrode plating, and dendrite growth. To address these issues, researchers have begun to examine the effects of various alterations to all‐iron RFBs, such as adding organic ligands to form Fe complexes and using a slurry electrode instead of common materials such as graphite or platinum rods. Overall, progress in improving aqueous all‐iron RFBs is at its infant stage, and new strategies must be introduced, such as the utilization of nanoparticles, which can limit dendrite growth while increasing storage capacity. This review provides an in‐depth overview of current research and offers perspectives on how to design the next generation of all‐iron aqueous RFBs.

Belongia, Shawn↗
DOE OSTI2021

Lanthanum induced lattice strain improves hydrogen sulfide capacities of copper oxide adsorbents

This work probes the effects of La on reactions involving CuO sorbents and H 2 S in gaseous streams. La-CuO sorbents with nominal La/Cu atomic ratios of 1:2 achieved higher capacities (27 and 36 g H 2 S per 100 g sorbent) compared to CuO sorbents (25 g H 2 S per 100 g sorbent). Here, comparison of the La-CuO sorbents using energy dispersive x-ray spectroscopy and La L 3 -edge XAS suggested that increased capacity resulted from more uniform dispersion of La within the CuO phase (3.3 wt.% vs. 1.0 wt.% La). X-Ray absorption near edge structure analysis suggested more electron-rich Cu species in La-CuO samples, while extended X-ray absorption fine structure modeling showed an increase in single-scattering path lengths for neighboring and near-neighbor atoms. These changes suggest that La induces strain in the Cu-O lattice, thereby increasing H 2 S capacity by reducing energy barriers associated with surface reactions between oxygen atoms and adsorbed H 2 S molecules.

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

Temporal Sampling of Enzymes from Live Cells by Localized Electroporation and Quantification of Activity by SAMDI Mass Spectrometry

Abstract Measuring changes in enzymatic activity over time from small numbers of cells remains a significant technical challenge. In this work, a method for sampling the cytoplasm of cells is introduced to extract enzymes and measure their activity at multiple time points. A microfluidic device, termed the live cell analysis device (LCAD), is designed, where cells are cultured in microwell arrays fabricated on polymer membranes containing nanochannels. Localized electroporation of the cells opens transient pores in the cell membrane at the interface with the nanochannels, enabling extraction of enzymes into nanoliter‐volume chambers. In the extraction chambers, the enzymes modify immobilized substrates, and their activity is quantified by self‐assembled monolayers for matrix‐assisted laser desorption/ionization (SAMDI) mass spectrometry. By employing the LCAD‐SAMDI platform, protein delivery into cells is demonstrated. Next, it is shown that enzymes can be extracted, and their activity measured without a loss in viability. Lastly, cells are sampled at multiple time points to study changes in phosphatase activity in response to oxidation by hydrogen peroxide. With this unique sampling device and label‐free assay format, the LCAD with SAMDI enables a powerful new method for monitoring the dynamics of cellular activity from small populations of cells.

Mukherjee, Prithvijit↗
DOE OSTI2023

Multi-atom Pt and PtRu catalysts for high performance AEMFCs with ultra-low PGM content

To reduce the platinum group metal (PGM) loading in anion exchange membrane fuel cells (AEMFCs), it is important to transition to catalysts with very low PGM content, and eventually to catalysts that are completely PGM-free. Here, in this work, four supported low-PGM Pt and PtRu catalysts were prepared using a new, simple, scalable technique: Controlled Surface Tension (CST) method. CST allows for a high density of very small multi-atom clusters. Catalysts were physically characterized using a wide array of techniques and tested for their ORR and HOR activity both ex-situ and integrated into operating AEMFCs. The PGM loading was reduced by a factor of 14 while achieving comparable performance to commercial catalysts. AEMFCs were also assembled with ultralow PGM loading (0.05 mgPGM cm -2 ), where PtRu anodes were paired with Fe–N–C cathodes to achieve a specific power of 25 W/mg PGM (40 W/mg Pt ).

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

Material Interactions in Severe Accidents – Benchmarking the MELCOR V2.2 Eutectics Model for a BWR-3 MARK-I Station Blackout: Part I – Single Case Analysis

Here in this analysis, the two material interaction models available in the MELCOR code are benchmarked for a severe accident at a BWR under representative Fukushima Daiichi boundary conditions. This part of the benchmark investigates the impact of each material interaction model on accident progression through a detailed single case analysis. It is found that the eutectics model simulation exhibits more rapid accident progression for the duration of the accident. The slower accident progression exhibited by the interactive materials model simulation, however, allows for a greater degree of core material oxidation and hydrogen generation to occur, as well as elevated core temperatures during the ex-vessel accident phase. The eutectics model simulation exhibits more significant degradation of core components during the late in-vessel accident phase – more debris forms and relocates to the lower plenum before lower head failure. The larger debris bed observed in the eutectics model simulation also reaches higher temperatures, presenting a more significant thermal challenge to the lower head until its failure. At the end of the simulated accident scenario, however, core damage is comparable between both simulations due to significant core degradation that occurs during the ex-vessel phase in the interactive materials model simulation. A key difference between the two models’ performance is the maximum temperatures that can be reached in the core and therefore the maximum ΔT between any two components. When implementing the interactive materials model, users have the option to modify the liquefaction temperature of the ZrO 2 -interactive and UO 2 -interactive materials as a way to mimic early fuel rod failure due to material interactions. Through modification of the liquefaction of high melting point materials with significant mass, users may inadvertently limit maximum core temperatures for fuel, cladding, and debris components.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

Chemically Controllable Porous Polymer–Nanocrystal Composites with Hierarchical Arrangement Show Substrate Transport Selectivity

Functional organic–inorganic hybrid materials with tunable properties are useful across many application areas, ranging from gas storage to electronics, flame retardants, separations, and catalysis. Combining polymers, with a suite of functional groups and conformational flexibility, and inorganic nanoparticles, with tunable surface chemistry and composition, yields hybrids with novel functional properties. Specifically, in catalysis, control of the electronic environment at a metal interface is paramount in determining the catalytic properties. In this contribution, we describe a modular process to prepare porous polymer–nanocrystal (NC) composites in a hierarchical, multilayered synthesis, in which multiple parameters can be accurately tuned: polymer functional groups and the corresponding pore structure, the polymer layer thickness, and the NC size, shape, and composition. This process provides for a variety of controlled materials with high surface area, tunable chemistry, and thermal and chemical stabilities. Furthermore, we demonstrate their utility for shape- and size-selective catalytic conversions both in oxidation and hydrogenation reactions, where they show increased selectivity by orders of magnitude compared to conventional polymer-supported metal catalysts. In light of the high degree of control in the composite structure, this method allows for the design and realization of catalysts for several reactions and reaction environments and for nanomaterials with other applications.

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

Predicting Oxygen Off-Stoichiometry and Hydrogen Incorporation in Complex Perovskite Oxides

Chemically and structurally complex solid compounds, including those with significant off-stoichiometry, are rapidly extending new material functionality across a variety of applications. Accelerated development of these compounds requires accurate predictions of material defect properties including effective defect formation energies and equilibrium defect concentrations. Traditional first-principles approaches typically examine dilute defect concentrations and relatively ordered atomic structures to identify the lowest energy defect sites. These approaches are rarely suitable for describing the disorder present in these systems and its influence on defect formation, which can lead to unphysically large predictions for defect concentrations. Here, we demonstrate a new method to accurately predict the temperature and pressure dependence of oxygen vacancy concentrations and proton interstitial concentrations in complex oxides. This method extends standard dilute defect calculations to incorporate atomic and magnetic disorder, employs the ensemble descriptions of defect sites resulting in improved predictions of defect formation energies, and accounts for effects beyond the dilute defect limit. To demonstrate our method, we show that the predicted defect concentrations in perovskites used as ceramic fuel cell cathodes, including Ba0.5Sr0.5Fe0.8Zn0.2O3-d, Ba0.5Sr0.5Co0.8Fe0.2O3-d, and BaCo1-x-y-zFexZryYzO3-d, are in good agreement with experimental values, thereby opening the door for predictive design of complex oxides by these applications.

DFT↗
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 OSTI2025

Proton Exchange Membrane (PEM) Water Electrolysis: Cell-Level Considerations for Gigawatt-Scale Deployment

Hydrogen produced with no greenhouse gas emissions is termed “green hydrogen” and will be essential to reaching decarbonization targets set forth by nearly every country as per the Paris Agreement. Proton exchange membrane water electrolyzers (PEMWEs) are expected to contribute substantially to the green hydrogen market. However, PEMWE market penetration is insignificant, accounting for less than a gigawatt of global capacity. Achieving substantive decarbonization via green hydrogen will require PEMWEs to reach capacities of hundreds of gigawatts by 2030. This paper serves as an overarching roadmap for cell-level improvements necessary for gigawatt-scale PEMWE deployment, with insights from three well-established hydrogen technology companies included. Analyses will be presented for economies of scale, renewable energy prices, government policies, accelerated stress tests, and component-specific improvements.

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

Enhanced Catalytic Performance of a Ce/V Oxo Cluster through Confinement in Mesoporous SBA-15

To increase catalytic efficiency, mesoporous supports have been widely applied to immobilize well-defined metal oxide clusters due to their ability to stabilize highly dispersed clusters. Here, for this study, a redox-active heterometallic Ce 12 V 6 -oxo cluster (CeV) was first presynthesized and then incorporated into mesoporous silica, SBA-15, via a straightforward impregnation method. Scanning transmission electron microscopy (STEM) and Fourier transform infrared spectroscopy (FTIR), in concert with scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDS), verified the successful introduction of the CeV cluster inside the pore of SBA-15. The 51 V magic angle spinning solid-state nuclear magnetic resonance ( 51 V MAS NMR) spectroscopy and differential pair distribution function (dPDF) analysis confirmed the structural integrity of the CeV cluster inside the SBA-15. The composite was then benchmarked for liquid-phase oxidation of 2-chloroethyl ethyl sulfide (CEES) under mild conditions and gas-phase oxidative dehydrogenation (ODH) of propane under high temperatures (up to 550 °C). The catalytic reactivity results demonstrated 8- and 14-fold increase in turnover frequency (TOF) values of the composite (CeV@10SBA-2) than the bulk CeV cluster under the same conditions for CEES oxidation and ODH, respectively. These results highlight the improved reactivity of the catalytically active CeV cluster as attributed to the higher dispersion of the discrete cluster upon immobilization within the SBA-15 support.

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

Nanoscopic Titanium Dioxide Overlayers Improve the Durability of Porphyrin Molecular Electrocatalysts while Maintaining Molecular Structure and Redox Activity

Molecular catalysts, such as metalated porphyrins, are attractive cocatalysts for photocatalytic water splitting owing to their potential to simultaneously catalyze target reactions at their metal center, extend charge-separated-state lifetimes, and accumulate the requisite charge for product formation. However, porphyrin catalysts, like most molecular catalysts, are often limited by poor stability associated with demetalation, inactivation by undesired bonding (e.g., O2 coordination/redox/dimerization), and detachment from electrode supports or semiconducting photoabsorbers. In this study, nanoscopic titanium dioxide (TiO2) overlayers, deposited by atomic layer deposition (ALD), are demonstrated to encapsulate cobalt(III) meso-tetra(4-carboxyphenyl) porphyrin chloride (CoTCPP) molecular catalysts and thereby improve their adhesion to electrode surfaces over a wide range of electrode potentials spanning from -1.0 V vs RHE to +1.8 V vs RHE. Through analysis of Raman and ultraviolet-visible spectroscopy, it was confirmed that the metalloporphyrin structure was maintained when the surface-bound CoTCPP was encapsulated by 10 - 250 ALD cycles (~2 - 18 nm thick) of TiO2. Additional characterization of CoTCPP catalysts before and after electrochemical measurements reveals that up to 97% of the encapsulated CoTCPP remains tethered to the electrode surface after chronoamperometry tests under hydrogen evolution reaction (HER) conditions, compared to <36% for unencapsulated CoTCPP. This study also shows that encapsulated CoTCPP molecules remain partially redox active for overlayers up to 8 nm, which can also attenuate undesired redox mediator back reactions like ferricyanide reduction.

08 HYDROGEN↗
DOE OSTI2025

Mesoporous Amorphous High-Entropy Oxide Films: Unlocking Enhanced Redox Activity

High-entropy oxides (HEOs) represent a frontier in catalyst design via entropy-stabilized solid solution formation. However, their catalytic efficiency is limited by their bulk and dense nature. This work presents a strategic approach to tackle this challenge by fabricating mesoporous amorphous HEO films (MA-HEOF) possessing maximized active site utilization efficiency. The success hinges on the as-developed geometric engineering strategy via controlled deposition–precipitation to confine the amorphous HEO thin film on the surface of mesoporous channels. The unique structure of MA-HEOF was elucidated via microscopy-, X-ray-, and neutron-based techniques, which were manifested by enriched surface-activated lattice oxygen and enhanced redox activity, as confirmed by isotope studies. Besides, the MA-HEOF could stabilize and modulate the properties of integrated noble metal sites, enhancing their redox activity in diverse reactions. In conclusion, the approaches and insights presented herein provide guidance on maximizing the utilization efficiency of high-entropy materials in catalysis and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Composition, Activity, and Stability of IrO x Oxygen Evolution Reaction Electrocatalysts

The oxygen evolution reaction (OER) is integral to several electrochemical energy conversion and storage technologies, including carbon dioxide reduction to value added fuels, nitrogen reduction to ammonia, reversible fuel cells, rechargeable metal−air batteries, and water electrolysis to produce hydrogen. Iridium oxide (IrO x ) is widely recognized as the benchmark OER catalyst for acidic environments. Despite widespread use of IrO x catalysts, most notably in proton-exchange membrane water electrolyzers (PEMWEs), a comprehensive understanding of the physicochemical properties of commercial catalysts and the impact of these properties on both the activity and stability of these catalysts is lacking. Here, we study commercial IrO x catalysts with different physicochemical properties, three nominally considered amorphous and three rutile, to elucidate how structural and compositional variations affect OER activity and stability. Utilizing standardized aqueous electrochemical protocols, time-resolved dissolution quantification using inductively-coupled plasma mass spectrometry, and physicochemical characterization, including multiple synchrotron X-ray techniques, we systematically correlate catalyst properties with OER performance and degradation behavior aided by principal component analysis (PCA). Our results demonstrate the general trend of amorphous IrO x having higher intrinsic activity but limited stability and crystalline rutile IrO 2 having lower activity but enhanced stability against dissolution. The trends within the amorphous and rutile catalyst groups correlate with inherent material properties, including phase composition and structure, crystallinity, particle size, surface area, and surface structure/chemistry. Notably, we identify a rutile catalyst with the largest crystallite/ domain sizes, moderate surface area, a small fraction of hydrous phase, and a favorable pore structure (trimodal distributions of pore sizes ranging from 2−5 nm) that exhibits the best balance between activity and stability among the six catalysts studied here. These findings illustrate a fundamental structure-governed trade-off between activity and stability and highlight the critical role of surface chemistry modification and structure engineering in IrO x catalyst optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗