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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 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Mitigation of hydrogen crossover in liquid alkaline water electrolysers using gas recombination catalysts

The rising demand for hydrogen calls for improvements in the efficiency of liquid alkaline water electrolysers (LAWEs), which can be fulfilled by advanced electrodes or separators. Nevertheless, they also intensify hydrogen crossover and safety concerns, thus mandating efficient mitigation strategies. Here we studied the correlation between cathodes and hydrogen crossover behaviours and mitigated safety risks by designing a gas recombination catalyst (GRC). We attribute the elevated hydrogen crossover associated with platinum-based cathodes to their preferential utilization for the hydrogen evolution reaction that creates elevated hydrogen supersaturation, as evidenced by direct measurements of dissolved hydrogen concentration. Varying the placement of platinum layers relative to the cathode–separator interface also supports this conclusion. The implementation of a GRC reduces hydrogen crossover by 95% without affecting LAWE performance and functions for over 1,000 h at 1 A cm−2. This study provides insights into hydrogen supersaturation and the crossover mechanism, as well as offering a promising pathway to enhance the efficiency and reliability of alkaline water electrolysis.

Liu, Haotian↗
DOE OSTI2026

Co-Design of Charge Transport Superhighways to Connect Catalytic Sites in Soft Photoelectrochemical Systems

Efficient photon-to-electron-to-molecule conversion requires multi-length scale control over charge transport pathways, where electronic charges are delivered to catalytic sites under high mass transport flux. A fundamental question is how can we co-design charge transport pathways to promote efficient charge transfer to/from catalytic sites in complex three-dimensional architectures? Soft conducting polymer systems offer exceptional promise to provide three-dimensional charge transport networks, where electrolyte (ion and solvent) can interdiffuse to promote long-lived charge carriers and the molecular nature allows for strategic synthetic design of catalytic sites. Herein we combine theoretical and experimental approaches to investigate the earliest stages of photoelectrochemical deposition of near-surface catalytic sites (Pt) on soft bulk heterojunction polymeric semiconductors composed of a prototype donor (PTB7-Th) and a prototype acceptor (N2200) as a model system towards better understanding molecular catalyst-polymer site interactions. We focus initially on photoelectrochemical deposition of low Pt loadings, nanoparticle sizes (formed by progressive nucleation) below 20 nm, for both density functional theory (DFT) modeling studies and for spectroscopic characterization using surface-sensitive X-ray and UV-photoemission (XPS/UPS). DFT modeling of “n-type” N2200 slabs reveal for the first time that sulfur atoms in the thiophene units serve as the lowest-energy adsorption sites for single Pt atoms, while larger Pt clusters engage more complexly with both thiophene and naphthalene diimide (NDI) core sites. Changes in chemical composition observed by X-ray photoelectron spectroscopy (XPS) support the DFT predictions, and the angle-resolved measurements reveal that Pt nucleation initiates at subsurface sites which appear to be localized active domains that promote charge transport/transfer and enable vertical growth toward the surface. These results suggest that light-activated Pt nanoparticle deposition decorates energetically distinct sites, where photoactivity is dictated by the local energetics of those sites, and the fact that they represent the termini of charge transport “super-highways” – a small percentage of the total volume of the donor/acceptor polymeric active layer which carries most of the photocurrent generated during both Pt deposition and photoelectrochemical HER. We posit that these initial studies provide a foundational strategy for design of catalytic sites in the near surface regions of complex polymeric materials and advancing soft semiconductor-based photoelectrochemical systems. Achieving a nanometer-scale understanding of catalyst deposition and the impact of local composition and energetics on that placement, should ultimately provide the design guidelines (co-design) for a broad array of catalysts at sites that optimize that efficiency and maximize platform durability.

14 SOLAR ENERGY↗
DOE OSTI2020

Antiferromagnetic Inverse Spinel Oxide LiCoVO 4 with Spin-Polarized Channels for Water Oxidation

Exploring highly efficient catalysts for the oxygen evolution reaction (OER) is essential for water electrolysis. Cost-effective transition-metal oxides with reasonable activity are raising attention. Recently, OER reactants' and products' differing spin configurations have been thought to cause slow reaction kinetics. Catalysts with magnetically polarized channels could selectively remove electrons with opposite magnetic moment and conserve overall spin during OER, enhancing triplet state oxygen molecule evolution. Herein, antiferromagnetic inverse spinel oxide LiCoVO 4 is found to contain d 7 Co 2+ ions that can be stabilized under active octahedral sites, possessing high spin states S = 3/2 (t 2g 5 e g 2 ). With high spin configuration, each Co 2+ ion has an ideal magnetic moment of 3 µ B , allowing the edge-shared Co 2+ octahedra in spinel to be magnetically polarized. Density functional theory simulation results show that the layered antiferromagnetic LiCoVO 4 studied contains magnetically polarized channels. The average magnetic moment (µ ave ) per transition-metal atom in the spin conduction channel is around 2.66 µ B . Such channels are able to enhance the selective removal of spin-oriented electrons from the reactants during the OER, which facilitates the accumulation of appropriate magnetic moments for triplet oxygen molecule evolution. Finally, the LiCoVO 4 reported has been identified as an oxide catalyst with excellent OER activity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Impact of Hydration on Supported V 2 O 5 /TiO 2 Catalysts as Explored by Magnetic Resonance Spectroscopy

Supported vanadium oxide catalysts are important industrial materials for a wide array of chemical transformations. The condition of surface hydration is of particular interest as a reflection of the state of a freshly manufactured catalysts prior to its activation in catalytic reactors or under conditions of photocatalysis where surface vandia are exposed to moisture. Under such conditions, the surface vanadia species undergo structural changes as evidenced by 51 V MAS NMR in this study. For low surface vanadia densities on titania, a modest trend towards the formation of dimeric and oligomeric vanadia species was observed under hydrated conditions when compared to the corresponding dehydrated catalyst, which contains a large abundance of monomeric vanadia species. The incorporation of tungsten oxide to the V 2 O 5 /TiO 2 catalyst with low surface vanadia density, however, is found to better stabilize the surface vanadia species on the titania support upon hydration than its tungsta-free counterpart. This stabilization is not an intrinsic property of more extensively oligomerized surface vanadia species in the presence of tungsten oxide, evidenced by conditions of high concentrations of surface vanadia oligomers on titania that exhibit dramatic structural changes upon hydration. At high surface vanadia coverage under hydrated environments, the simultaneous observation of crystalline V 2 O 5 nanoparticles and a mobile phase of surface vanadia species is apparent, where vanadia species are dissolved in the thin hydration layer on the titania support. These new findings have broad implications on the behavior of other metal oxide species on high surface oxide supports under hydrated conditions.

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

Stable Solid Electrolyte Interphase Layer Formed by Electrochemical Pretreatment of Gel Polymer Coating on Li Metal Anode for Lithium–Oxygen Batteries

Lithium (Li)-oxygen (O2) batteries (LOBs) exhibit the highest theoretical specific energy density among candidates of the next-generation energy storage systems, but the instability of Li metal anode (LMA), air electrode, and electrolyte largely limit the practical energy density of these batteries. Herein, we report an effective method to protect LMA against side reactions between LMA and crossover contaminants such as highly reactive oxygen moieties. A solid electrolyte interphase (SEI) layer rich in inorganic components was formed on a LMA coated with polyethylene oxide thin-film through an in-situ electrochemical pre-charging step under oxygen atmosphere. This uniformly distributed stiff SEI layer interacted with flexible polymer matrix and formed a submicron-sized gel-like polymer layer. This polymer supported SEI layer leads to much longer cycle life (130 vs. 65 cycles) as compared to those of pristine cell under the same testing conditions (1.0 mAh cm-2 at 0.2 mA cm-2 in the voltage range of 2 to 5 V without any catalysts). It is also very effective during low voltage (2 to 4.5 V) cycling with a redox mediator (0.1 and 0.15M (2,2,6,6-tetramethylpiperidin-1-yl) oxidanyl). Therefore, this approach can be used to stabilize LMA/electrolytes interphase and improve the cycle life of rechargeable LOBs.

lithium-oxygen batteries, lithium metal anodes, ar↗
DOE OSTI2025

Volumetric Additive Manufacturing of Dormant Catalytic Chemistries to Generate Silicone Micro‐ and Millifluidic Devices and Instant Molds

Tomographic volumetric additive manufacturing (T‐VAM) rapidly prints solid objects within minutes, accessing photochemistries that are traditionally challenging for layer‐based additive manufacturing methods. This includes high‐viscosity materials, air‐free chemistries, and solid‐state systems. Catalytic chemistries are appealing as a pathway to engineering advanced materials, including tough thermosets, silicone elastomers, and complex block copolymers. However, photoactivated dormant catalytic chemistries, where the catalyst irreversibly activates upon exposure to light, are incompatible with typical tomographic VAM approaches. To address this limitation, a zero‐dose optimization strategy is devised to preserve dormant catalysts in desired regions by keeping them unexposed to light. VAM printed micro‐ and millifluidic devices and instant molds are successfully produced within minutes in silicones polymerized using photoactivated dormant platinum photohydrosilylation catalysts. The printed channels are programmed to be 500 and 2500 µm for the micro‐ and millifluidic devices, and print fidelity is assessed by X‐ray computed tomography. This work demonstrates the potential of zero‐dose optimization to expand the range of chemistries accessible for VAM, enabling the rapid fabrication of complex devices.

Additive Manufacturing↗
DOE OSTI2023

Lithium superoxide-based high rate Li-Air batteries enabled by Di-iridium sulfur bridge active sites

Li-oxygen (Li-O 2 ) batteries can potentially provide much higher energy density than Li-ion batteries; however, the practical application of these batteries is hindered due to several drawbacks such as low current rates and high overpotential for the charging process. Here, in this paper, we report a novel Li-Air battery system that operates under high current rates (up to 1mAcm -2 ) with LiO 2 as the primary discharge product instead of the commonly reported Li 2 O 2 . This LiO 2 based battery at high rates is through a combination of an as-synthesized new one-dimensional (1D) transition metal trichalcogenide mid-entropy alloy of SnIrS 3.6 as a cathode catalyst and an electrolyte blend with a SnI 2 bi-functional additive. It is revealed that SnIrS 3.6 has a microporous structure composed of six- and five-coordinated metal atoms, forming octahedral and triangular bipyramids which has not been observed in other layered chalcogeide materials. DFT calculations reveal that the SnIrS 3.6 structure can result in LiO 2 formation through di-iridium sulfur bridge active sites that results in strong binding of O 2 and LiO 2 preventing disproportionation to Li 2 O 2 and enabling high rates. This finding will open a new perspective in designing advanced LiO 2 -based Li-O 2 batteries for real practices.

25 ENERGY STORAGE↗
DOE OSTI2023

High Efficiency PEM Water Electrolysis Enabled by Advanced Catalysts, Membranes and Processes

In this project, advanced membranes and catalysts were integrated into membrane electrode assembles (porous transport electrodes (PTE) or catalyst coated membranes (CCM)) leveraging precision coating methods to enable control of electrode structures and demonstration of the best component performance possible with these materials. Partner collaborations allowed for advanced characterization of the formed interfaces and degradation mechanisms. New methods of forming hydrogen recombination layers were also developed, to move away from wet chemistry processes that would have limited realization and implementation of the optimized electrode configurations in a commercial environment.

08 HYDROGEN↗
DOE OSTI2022

3D-printed electrode, gas diffusion electrode (GDE) and gas diffusion layer (GDL) for fuel cell applications

An electrocatalytically active ink composition is used with an additive manufacturing process, such as 3D printing, to produce electrodes having consistent, adaptable, and high surface area structures. The electrocatalytically active ink composition includes a mixed powdered precursor and a polymer matrix. The mixed powdered precursor includes a carbon source, a dopant source, and/or a metal-containing catalyst. The material and electrochemical properties of the ink composition may facilitate 3D printing of electrochemically active electrodes for energy conversion and storage devices, and may allow fine-tuning of macro- and microstructures to develop electrodes having improved activity and efficiency.

Lee, Kwan-Soo↗
DOE OSTI2020

Electronic structure and oxophilicity optimization of mono-layer Pt for efficient electrocatalysis

The slow kinetics of the anodic hydrogen oxidation reaction (HOR) in alkaline medium is one of the limitations for anion exchange membrane fuel cells (AEMFCs). Hence, accurately regulate and understand catalytic interface structure are essential to solve this bottleneck and reveal the structure-activity relationship. In this work, a novel trimetal core-shell model with mono-layer Pt-shell is employed for hydrogen electrooxidation to avoid thermodynamic driven bulk/surface composition deviation. On account of the atomic radius discrepancies of 3d-transition metals M (M = Fe, Co and Cu), the electronic structure of mono-layer Pt is regulated by the strain-engineered Pd-M core and the electrocatalytic activity for HOR is tuned accordingly. Nevertheless, step-by-step electrochemical monitoring and surface-treatment experiments indicate that the oxophilicity optimization by low-valence M(OH) x species, rather than the hydrogen binding energy (HBE) optimization caused by strain engineering, influence the activity obviously. It is mainly derived from the enhanced adsorption of OH ad and accelerated desorption of the H ad . The trimetal core-shell model breathes new life into the low-Pt catalyst design for hydrogen electrooxidation reaction.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Dry reforming of methane over Ni supported on LaMnO 3 thin films

Thin films of LaMnO 3 were deposited onto MgAl 2 O 4 by Atomic Layer Deposition (ALD) and studied as supports for Ni in the Dry Reforming of Methane (DRM). Scanning Transmission Electron Microscopy (STEM) with Energy-Dispersive X-ray Spectroscopy (EDS) demonstrated that LaMnO 3 covered the support uniformly, and X-ray diffraction (XRD) showed that the LaMnO 3 films maintained their perovskite structure after 5 redox cycles at 1073 K. The Ni also remained well dispersed after 5 redox cycles at 1073 K. The LaMnO 3 -supported catalyst was more active than Ni on the unmodified MgAl 2 O 4 and showed superior resistance against coke formation. Lastly, the results for Ni on the LaMnO 3 films are compared to previous results for Ni on LaFeO 3 , CaTiO 3 , SrTiO 3 , and BaTiO 3 films.

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

Experimental Verification of Ir 5d Orbital States and Atomic Structures in Highly Active Amorphous Iridium Oxide Catalysts

In iridium oxide catalysts, the electronic states whose energies are in the range of energetics and charge transfer kinetics of the oxygen evolution reaction (OER) originate from the Ir 5d orbital states. However, the understanding of the atomic structures and orbital states underlying catalytic reactivity in amorphous iridium oxide oxygen evolving catalysts (Ir-OECs) is incomplete compared to that of crystalline oxides, owing to a lack of direct experimental verification. Here, we present experimental approaches using resonant inelastic X-ray scattering (RIXS) to directly access Ir 5d orbital excitations at the Ir L 3 edge and atomic pair distribution function (PDF) measurements to characterize electronic and coordination structures at the atomic scale. The so-called iridium blue layer (IrBL) and IrO x were formed from the organometallic precursor complex [Cp*Ir(H 2 O) 3 ]SO 4 and the inorganic precursor IrCl 3 , respectively. Ex situ IrBL and IrO x films for RIXS and PDF measurements were prepared by conditioning electrodeposited films at a low voltage. The incident energy RIXS profile of IrO x exhibited extra weak resonantly enhanced excitation below 2 eV energy loss. The feature was clearly different from a single high-energy excitation above 3 eV of IrBL related to the interband transition between π- and σ-antibonding states. The atomic structure refinement based on PDF measurements revealed the atomic structure domains to have edge- and corner-shared IrO 6 octahedra with trigonal-type distortion. Furthermore, density functional theory calculations guided by the refined atomic structures shed light on the electronic structure corresponding to experimental results, including insulating and metallic phases in ex situ IrBL and IrO x films, respectively. Our study establishes different Ir 5d orbital states and atomic structures in two amorphous Ir oxide OER catalysts in their reduction states.

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

Oxygen Adsorption, Subsurface Oxygen Layer Formation and Reaction with Hydrogen on Surfaces of a Pt–Rh Alloy Nanocrystal

The oxygen adsorption and its catalytic reaction with hydrogen on Pt–Rh single crystals were studied at the nanoscale by Field Emission Microscopy (FEM) and Field Ion Microscopy (FIM) techniques at 700 K. Both FEM and FIM use samples prepared as sharp tips, apexes of which mimic a single nanoparticle of catalyst considering their similar size and morphology. Oxygen adsorption on Pt-17.4 at.%Rh samples leads to the formation of subsurface oxygen, which is manifested in the field emission (FE) patterns: for O2 exposure of ~3 Langmuir (L), {113} planes appear bright in the emission pattern, while for higher oxygen doses, i.e. 84 L, the bright regions correspond to the high index planes between the {012} and {011} planes. Formation of subsurface oxygen is probably accompanied by a surface reconstruction of the nanocrystal. The subsurface oxygen can be effectively reacted off by subsequent exposure of the sample to hydrogen gas at 700 K. The hydrogenation reaction was observed as a sudden, eruptive change of the brightness seen on the FE pattern. This reaction resulted in the recovery of the initial field emission pattern characteristic of a clean tip, with {012} facets being the most visible. It was shown that the oxygen accumulation-reduction process is completely reversible. The obtained results indicate that the presence of subsurface species must be considered in the description of reactive processes on Pt–Rh catalysts.

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

Expanding Access to Science Participation: A FAIR Framework for Petascale Data Visualization and Analytics

The massive data generated by scientists daily serve as both a major catalyst for new discoveries and innovations, as well as a significant roadblock that restricts access to the data. Here, our paper introduces a new approach to removing Big Data barriers and democratizing access to petascale data for the broader scientific community. Our novel data fabric abstraction layer allows user-friendly querying of scientific information while hiding the complexities of dealing with file systems or cloud services. We enable FAIR (Findable, Accessible, Interoperable, and Reusable) access to datasets such as NASA’s petascale climate datasets. Our paper presents an approach to managing, visualizing, and analyzing petabytes of data within a browser on equipment ranging from the top NASA supercomputer to commodity hardware like a laptop. Our novel data fabric abstraction utilizes state-of-the art progressive compression algorithms and machine-learning insights to power scalable visualization dashboards for petascale data. The result provides users with the ability to identify extreme events or trends dynamically, expanding access to scientific data and further enabling discoveries. We validate our approach by improving the ability of climate scientists to visually explore their data via three fully interactive dashboards. We further validate our approach by deploying the dashboards and simplified training materials in the classroom at a minority-serving institution. These dashboards, released in simplified form to the general public, contribute significantly to a broader push to democratize the access and use of climate data.

Computer science↗
DOE OSTI2024

Additive manufacturing of hierarchical three- dimensional micro-architected aerogels

Disclosed here is a method for making a three-dimensional micro-architected aerogel, comprising: (a) curing a reaction mixture comprising a co-sol-gel material (e.g., graphene oxide (GO)) and at least one catalyst to obtain a crosslinked co-sol-gel (e.g., GO hydrogel); (b) providing a photoresin comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of the crosslinked co-sol-gel (e.g., GO hydrogel); (c) curing the photoresin using projection microstereolithography layer-by-layer to produce a wet gel having a pre-designed three-dimensional structure; (d) drying the wet gel to produce a dry gel; and (e) pyrolyzing the dry gel to produce a three-dimensional micro-architected aerogel (e.g., graphene aerogel). Also disclosed is a photoresin for projection microstereolithography, comprising a solvent, a photoinitiator, a crosslinkable polymer precursor, and a dispersion of a crosslinked co-sol-gel.

Worsley, Marcus A.↗
DOE OSTI2022

Dependency of CO 2 methanation on the strong metal-support interaction for supported Ni/CeO 2 catalysts

The strong metal-support interaction (SMSI) for supported Ni/CeO 2 catalysts with different CeO 2 nanomorphologies was systematically explored. The degree of encapsulation of Ni particles originating from the SMSI effect was found to follow the trend of Ni/CeO 2 -(1 1 1) > Ni/CeO 2 -(1 0 0) > Ni/CeO 2 -(110 + 100), which parallels the CO 2 hydrogenation activity. Quasi in situ XPS reveals the presence of Ce 3+ sites in accordance with the formation of an amorphous surface CeOx layer encapsulating the Ni nanoparticles. In situ DRIFTS indicates the reaction pathway and rate-determining step are dependent on the degree of the SMSI effect, leading to distinct selectivities towards CH 4 , especially at a high weight hourly space velocity (WHSV). Finally, these findings present a fundamental strategy about tailoring catalytic performance through support facet dependent susceptibility of SMSI phenomena.

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

Isopotential Electron Titration of Ammonia Charge Transfer on Metal Catalysts

Electron transfer between adsorbates and surfaces determines the binding strength and reactivity of chemical moieties on materials designed for separations and catalysis. To quantify electron exchange, the extent of charge transfer resulting from ammonia adsorption on a Ru surface was measured by isopotential electron titration (IET) on a Ru catalytic condenser, where isopotential conditions were maintained between Ru and silicon separated by an insulating HfO 2 layer during gas phase ammonia adsorption. Charge transfer upon ammonia adsorption on a Ru catalytic condenser increased from 40 to 1200 nC/cm 2 at 75 and 225 °C, respectively. Charge transfer measurements provided a direct estimate of ammonia adsorption thermodynamics on Ru without knowing surface coverages a priori, revealing an adsorption enthalpy of −53 ± 10 kJ/mol and entropy of −61 ± 26 J/mol·K. Combining experimentally-measured charge transfer with kinetic Monte Carlo simulations informed adsorbate surface coverages determined that 0.058 electrons were transferred to the Ru surface for each molecular ammonia adsorption event (δ NH 3 = 0.058 ± 0.005 e – /NH 3 *), consistent with calculated Bader charges. The ability to measure the extent of charge transfer for adsorbed species provides a fundamental descriptor to understand existing and new chemically functional surfaces, providing a foundational method for the emerging field of thermochemical surface coulometry.

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

Polyethylene Upcycling to Diacids Using Acid-Only Activation

There is a pressing need to develop plastic recycling technologies. Chemical upcycling converts low-value waste plastics into higher-value products. Here, polyethylene (PE) upcycling is accomplished by using acid-only activation of PE (PEAA), thus eliminating costly and toxic organic solvents. Acid mixtures of chlorosulfuric acid (CSA) and sulfuric acid (SA) were used to effectively sulfonate PE, allowing for subsequent facile depolymerization. Molecular deconstruction of sulfonated PE using H 2 O 2 in the presence of an Fe(III) catalyst achieved molar yields of C 2 –C 4 diacids exceeding 40% (based on estimates of acids generated from sulfonates). The sulfonation step using PEAA is hypothesized to follow a shrinking core mechanism (SCM), in which PE particles quickly reach a saturated state in the outer sulfonated layer as CSA diffuses radially inward. This proposed mechanism is supported by the fact that, regardless of the extent of sulfonation, similar molar yields of products and ratios of liberated carbon to sulfur are observed. Modeling and experimentation show that deviations from the SCM occur by lowering the Damköhler number (Da) or increasing CSA solubility in PE. In both cases, CSA diffusion is enhanced, which favors kinetically limited sulfonation.

36 MATERIALS SCIENCE↗