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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 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Effects of Sodium and Tungsten Promoters on Mg 6 MnO 8 -Based Core–Shell Redox Catalysts for Chemical Looping—Oxidative Dehydrogenation of Ethane

The present study investigates the effect of sodium and tungsten promoters on Mg 6 MnO 8 -based redox catalysts in a chemical looping oxidative dehydrogenation (CL-ODH) scheme. CL-ODH has the potential to significantly lower energy consumption and CO 2 /NO x emissions for ethylene production compared with conventional steam cracking. Sodium tungstate (Na 2 WO 4 ) was previously shown to be an effective promoter for Mg 6 MnO 8 -based redox catalysts. Overall, the CL-ODH reaction proceeds via parallel gas-phase cracking of ethane and selective combustion of H 2 on the surface of the Na 2 WO 4 -promoted redox catalyst. Reaction testing indicates that both Na and W are necessary to form Na 2 WO 4 and to achieve high ethylene selectivity. A Na:W ratio lower than 2:1 lead to significant formation of additional mixed tungsten oxide phases and decreases ethylene selectivity. Further characterizations based on low-energy ion scattering (LEIS) and differential scanning calorimetry (DSC) indicate that the NaW promoter forms a molten shell around the Mg6MnO8 redox catalyst. Methanol TPSR and in situ DRIFTS experiments indicate that the promoter significantly suppresses the number of basic sites on Mg 6 MnO 8 . 18 O– 16 O exchange experiments reveal that the promoter decreases the rate of oxygen exchange. O 2 cofeed studies indicate that below the melting temperature of Na 2 WO 4 , H 2 and CO conversions are both inhibited, but above the melting temperature, H 2 combustion significantly increased while CO combustion is still inhibited. On the basis of extensive characterizations, it was determined that H 2 is primarily combusted at the gas–Na 2 WO 4 molten shell interface via redox reactions of the tungsten salt, likely between the WO 4 2– (tungstate) and WO 3 – (tungsten bronze).

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

Designing the Platinum Catalyst Layer for Improved Performance and Durability in Anion Exchange Membrane Water Electrolysis

To lower the cost of hydrogen produced by anion exchange membrane water electrolysis (AEMWE), it is critical to reduce the use of platinum group metal (PGM) catalysts within the device. While iridium has been successfully replaced with PGM-free catalysts at the anode, platinum-based (Pt) cathode catalysts are still required to meet the activity and durability targets. This study investigates the impact of commercial Pt/C catalyst loading, ionomer type and content, and electrode fabrication method on the cathode catalyst layer properties and AEMWE performance with the aim of determining the feasibility of reduced Pt loadings. While increased Pt loading is found to improve beginning-of-life performance, the effects are minimal above 0.6 mg/cm 2 . Ink characterization shows that ionomer type and content affect the ink stability, particle size, and percent of unbound ionomer, which further impact the homogeneity of the sprayed catalyst layers. The 5% PiperION cathode exhibited the highest performance, which may be attributed to a balance between the small particle size and the low proportion of unbound ionomer, minimizing kinetic and transport losses. Theoretical calculations show that the ionomers interact differently with the Pt surface, causing different surface charges and water adsorption strength and activating different mechanisms for hydrogen evolution. Pt-PiperION lowered the enthalpy of water-splitting by 0.1 eV compared to Pt alone and allowed for equal site access between adsorbed H* and OH* (both adsorbed at circa −2.2 eV). Although catalyst-coated membrane (CCM) fabrication techniques are desirable for scale-up, no performance enhancement is observed compared with the catalyst-coated substrate approach. Durability, as measured by degradation rates, Pt loss, and catalyst layer restructuring, was found to improve with increased Pt loadings, higher ionomer content, and CCM architectures. These findings provide important insight into the significant role of the cathode in AEMWE and strategies for maintaining the performance with low Pt loading or PGM-free catalysts.

08 HYDROGEN↗
DOE OSTI2026

Elucidating the role of surface species in CO oxidation catalyzed by boron nitride nanotube supported transition metal oxides

Boron nitride nanotube (BNNT) is considered a highly promising catalyst support due to its outstanding thermal stability and chemical inertness. These characteristics make BNNT an attractive alternative for high-temperature applications. However, most studies to date have focused on incorporating platinum group metals (PGMs) to achieve high activity. Although BNNT-supported PGM catalysts are highly effective, their scarcity and high cost hinder widespread use in industrial processes. In this study, BNNT-supported transition metal oxides (TMO x /BNNT; TM = Fe, Co, Ni, and Cu) catalysts were investigated, and CO oxidation was applied as a model reaction to evaluate their catalytic performance. Several characterization techniques, including SEM-EDX, TEM, SXRD, H 2 -TPR, and XPS, were employed to examine their physicochemical properties. Notably, the particle size of the metal oxides differed significantly depending on the metal type. This variation is primarily attributed to the inherent metal–support interactions and the thermodynamic stability of each oxide during synthesis. These properties also affected catalytic activity, and various parameters, such as oxygen mobility and redox behavior, played important roles in determining performance. Finally, in situ DRIFTS, CO-TPSR, reaction-order analysis, and 18 O 2 isotope-labeling experiment were used to investigate the reaction mechanism. In conclusion, the findings provide insights into the design of cost-effective BNNT-supported catalysts and highlight their potential applicability in oxidation reactions.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. In conclusion, this discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.

08 HYDROGEN↗
DOE OSTI2015

Engineering catalytic activity via ion beam bombardment of catalyst supports for vertically aligned carbon nanotube growth

Carbon nanotube growth depends on the catalytic activity of metal nanoparticles on alumina or silica supports. The control on catalytic activity is generally achieved by variations in water concentration, carbon feed, and sample placement on a few types of alumina or silica catalyst supports obtained via thin film deposition. We have recently expanded the choice of catalyst supports by engineering inactive substrates like c-cut sapphire via ion beam bombardment. The deterministic control on the structure and chemistry of catalyst supports obtained by tuning the degree of beam-induced damage have enabled better regulation of the activity of Fe catalysts only in the ion beam bombarded areas and hence enabled controllable super growth of carbon nanotubes. A wide range of surface characterization techniques were used to monitor the catalytically active surface engineered via ion beam bombardment. The proposed method offers a versatile way to control carbon nanotube growth in patterned areas and also enhances the current understanding of the growth process. As a result, with the right choice of water concentration, carbon feed and sample placement, engineered catalyst supports may extend the carbon nanotube growth yield to a level that is even higher than the ones reported here, and thus offers promising applications of carbon nanotubes in electronics, heat exchanger, and energy storage.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2019

Low-Platinum Group (PGM) Metal Catalysts (Final Report)

High catalyst loadings and relatively high over-potential losses have limited the commercial viability of direct methanol fuel cells (DMFCs). Platinum-based catalysts are used in DMFCs with a loading of 4.5 mg cm-2; the catalyst layer is a significant contributor to the membrane electrode assembly (MEA) cost, which accounts for 60% of the system cost. The large-scale commercial viability of DMFCs is dependent on a significant (~50%) cost reduction. If these cost goals can be reached, the current market can be extended from 100's of units to 10,000's of units. Currently, Oorja is using a platinum-ruthenium catalyst for methanol oxidation, but does not have access to a supplier able to develop low-platinum group (PGM) metal catalysts to reach DMFC cost reduction targets. Oorja has recently developed a small lab scale capability in fabrication and testing of DMFC membrane electrode assemblies (MEAs), but does not have access to synthesis and characterization of advanced electrocatalysts. The materials, equipment, and expertise at the National Renewable Energy Laboratory (NREL) are of significant value to Oorja. NREL recently develop platinum-nickel nanowires as catalysts in hydrogen fuel cells. These materials have also shown promise in DMFC applications as a potential replacement for standard platinum-ruthenium catalysts; in ex-situ testing, these materials have shown one order of magnitude higher mass activity and can avoid ruthenium crossover contamination effects. These combined properties are exceptionally appealing to Oorja, and can result in significantly decreasing the capital costs of DMFCs.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

Anion Exchange Membrane Water Electrolysis Using a Catalyst-Coated Membrane Cathode

A catalyst-coated membrane (CCM) approach to electrode fabrication for high pH water electrolysis offers enhanced interfacial contact between the catalyst layer and the membrane surface in comparison to the catalyst-coated substrate (CCS) electrode configuration. The CCM facilitates enhanced ionic and water transport between the cathode and the anion exchange membrane (AEM). This advantage is particularly significant with AEM water electrolysis (compared to proton exchange membrane water electrolysis) because the cathode typically operates under dry conditions and relies solely on diffusive water transport across the AEM from the liquid-fed anode. This study presents a direct performance comparison between CCS and CCM cathode configurations using identical hydrogen evolution reaction (HER) catalysts and other components. The use of a pseudo-reference electrode integrated into the membrane electrode assembly enabled detailed analysis of the CCM cathode polarization behavior. Surface characterization provided insight into the degradation mechanisms associated with the CCM configuration. Optimization of the cathode ionomer cross-link density improved both the cathode polarization performance and the electrolysis device durability. Further optimization of the HER catalyst loading in the CCM cathode resulted in additional gains in the electrolysis efficiency. Collectively, these findings offer valuable guidance for the design and fabrication of high-performance, durable AEM electrolysis CCMs.

Water electrolysis↗
DOE OSTI2019

Metallopolymerization as a Strategy to Translate Ligand-Modulated Chemoselectivity to Porous Catalysts

Porous catalysts have garnered substantial interest as potential platforms for group-transfer catalysis due to the ability to noncovalently colocalize substrates in proximity to site-isolated reactive intermediates. In contrast to soluble molecular catalysts, the limited synthetic toolbox available to prepare porous catalysts presents a formidable challenge to controlling the primary coordination sphere of lattice-confined catalysts and thus modulating the electronic structures of reactive catalyst intermediates. Here, we utilize Sonogashira cross-coupling chemistry to prepare a family of porous metallopolymers in the primary coordination sphere of Ru 2 sites. The newly synthesized materials are characterized by IR, elemental analysis, gas sorption, powder X-ray diffraction, thermogravimetric analysis, X-ray absorption spectroscopy, and diffuse-reflectance UV–vis-NIR spectroscopy. The resulting porous materials are catalysts for nitrene-transfer chemistry, and the chemoselectivity for allylic amination versus olefin aziridination can be tuned by modulating the primary coordination sphere of the catalyst sites. Furthermore, the demonstration of metallopolymerization as a rational synthetic strategy enables ligand-modulated chemoselectivity to be achieved with porous catalysts and represents a new opportunity to tailor the functionality of heterogeneous catalyst materials.

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

Atomically Dispersed Dual‐Metal Site Catalysts for Enhanced CO 2 Reduction: Mechanistic Insight into Active Site Structures

Abstract Carbon‐supported nitrogen‐coordinated single‐metal site catalysts (i.e., M−N−C, M: Fe, Co, or Ni) are active for the electrochemical CO 2 reduction reaction (CO 2 RR) to CO. Further improving their intrinsic activity and selectivity by tuning their N−M bond structures and coordination is limited. Herein, we expand the coordination environments of M−N−C catalysts by designing dual‐metal active sites. The Ni‐Fe catalyst exhibited the most efficient CO2RR activity and promising stability compared to other combinations. Advanced structural characterization and theoretical prediction suggest that the most active N‐coordinated dual‐metal site configurations are 2N‐bridged (Fe‐Ni)N 6 , in which FeN 4 and NiN 4 moieties are shared with two N atoms. Two metals (i.e., Fe and Ni) in the dual‐metal site likely generate a synergy to enable more optimal *COOH adsorption and *CO desorption than single‐metal sites (FeN 4 or NiN 4 ) with improved intrinsic catalytic activity and selectivity.

Li, Yi↗
DOE OSTI2020

Self-grown NiCuO x hybrids on a porous NiCuC substrate as an HER cathode in alkaline solution

Electrocatalysts converted directly from the substrates hold the key to achieve high catalytic activity and durability due to their high bonding strength, intimate electronic contact, and tunable phase composition. Herein, an electrically conductive porous NiCuC substrate was adopted to develop a multi-porous NiCuO x /NiCuC hydrogen evolution reaction (HER) catalyst using a one-step oxidation method in this research. The NiCuO x hybrids were characterized as three typical layers: an outer layer with NiCuO 2 solid solution phase, a partially oxidized intermediate layer, and an inner layer with limited stable oxygen content. Here, the NiCuO x /NiCuC possesses abundant Ni(II)–Cu(II) sites to accelerate the Volmer step via the electrostatic effect with OH – , numerous metallic NiCu sites to facilitate the H adsorption, and highly accessible channels to promote the Heyrovsky step during HER catalysis. As a result, high electrocatalytic performance was obtained with an overpotential of 116 mV at a current density of 10 mA cm –2 in 1.0 M potassium hydroxide, and a stable catalytic performance during the HER process for more than 24 h.

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

Tuning the Molecular Structure and Reaction Mechanism of Olefin Metathesis by Model Bilayered Supported MoO x /AlO x /SiO 2 Catalysts

The molecular structure and activity of supported MoO x olefin metathesis catalysts are heavily impacted by the choice of catalyst support. In this study, surface modification of the SiO 2 support with AlO x and selective anchoring of the MoO x on the surface AlO x sites were used to tune the structure, activation, and reactivity of the resulting surface MoO x sites. Extensive in situ molecular characterization, chemical probe studies, and density functional theory (DFT) calculations reveal that the enhanced activity of the supported MoO x /AlO x /SiO 2 catalyst over the MoO x / SiO 2 catalyst is associated with more favorable activation and kinetics of surface MoO x anchored at AlO x sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Carbon nanospikes grown on metal wires as microelectrode sensors for dopamine

Carbon nanomaterials are advantageous as electrodes for neurotransmitter detection, but the difficulty of nanomaterials deposition on electrode substrates limits the reproducibility and future applications. In our study, we used plasma enhanced chemical vapor deposition (PECVD) to directly grow a thin layer of carbon nanospikes (CNS) on cylindrical metal substrates. No catalyst is required and the CNS surface coverage is uniform over the cylindrical metal substrate. We characterized the CNS growth on several metallic substrates including tantalum, niobium, palladium, and nickel wires. Using fast-scan cyclic voltammetry (FSCV), bare metal wires could not detect 1 mu M dopamine while carbon nanospike coated wires could. Moreover, the highest sensitivity and optimized S/N ratio was recorded from carbon nanospike-tantalum (CNS-Ta) microwires grown for 7.5 minutes, which had a LOD of 8 +/- 2 nM for dopamine with FSCV. CNS-Ta microelectrodes were more reversible and had a smaller Delta E-p for dopamine than carbon-fiber microelectrodes, suggesting faster electron transfer kinetics. The kinetics of dopamine redox were adsorption controlled at CNS-Ta microelectrodes and repeated electrochemical measurements displayed stability for up to ten hours in vitro and over a ten day period as well. The oxidation potential was significantly different for ascorbic acid and uric acid compared to dopamine. Finally, growing carbon nanospikes on metal wires is a promising method to produce uniformly-coated, carbon nanostructured cylindrical microelectrodes for sensitive dopamine detection.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Insights into CO 2 adsorption and chemical fixation properties of VPI-100 metal–organic frameworks

Here, metal–organic frameworks (MOFs) have shown great promise as efficient CO 2 adsorbents, as well as an emerging class of heterogeneous catalysts for conversion of CO 2 to other useful chemicals. In this work, we synthesized and characterized two isostructural hafnium-based MOFs, denoted as Hf-VPI-100 (Cu) and Hf-VPI-100 (Ni). Both frameworks demonstrated high catalytic efficiency for cycloaddition of CO 2 to epoxides under ambient pressure. In situ PXRD, QCM and DRIFTs have been used to probe the interaction between the guest molecules (CO 2 /epoxide) and Hf-VPI-100. The crystal structures of these frameworks were preserved during the exposure to CO 2 atmosphere up to 20 bar. The epoxide uptake per unit cell of VPI-100 and diffusion coefficients have been calculated by QCM analysis. Comparison of catalytic efficiency between Hf-VPI-100 and the previously reported Zr-based VPI-100, aided by electronic structure calculations revealed that the open metal centers in the metallocyclam act as the primary Lewis acid sites to facilitate the catalytic conversion of CO 2 .

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

Catalytic activation of ethylene C–H bonds on uniform d 8 Ir( I ) and Ni( II ) cations in zeolites: toward molecular level understanding of ethylene polymerization on heterogeneous catalysts

The homolytic activation of the strong C–H bonds in ethylene is demonstrated, for the first time, on d 8 Ir(I) and Ni(II) single atoms in the cationic positions of zeolites H-FAU and H-BEA under ambient conditions. The oxidative addition of C 2 H 4 to the metal center occurs with the formation of a d 6 metal vinyl hydride, explaining the initiation of the olefin-polymerization cycle on d 8 M(I/II) sites in the absence of pre-existing M–H bonds. Under mild reaction conditions (80–220 °C, 1 bar), the catalytic dimerization to butenes and dehydrogenative coupling of ethylene to butadiene occurs over these catalysts. 1-Butene is not converted to butadiene under the reaction conditions applied. Post-reaction characterization of the two materials reveals that the active metal cations remain site-isolated whereas deactivation occurs due to the formation of carbonaceous deposits on the zeolites. Here, our findings have significant implications for the molecular level understanding of ethylene conversion and the development of new ways to functionalize C–H bonds under mild conditions.

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

Evaluation of Attractive Interactions in the Second Coordination Sphere of Iron Complexes Containing Pendant Amines

The interactions between pendant amines in the second coordination sphere and ligands in the first coordination sphere are important for understanding the structures and reactivity of complexes containing PR2NR'2 ligands, which have been shown to be highly active H2 oxidation/production catalysts. A series of [Fe(PPh2NBn2)2(X)(Y)]n+ complexes have been prepared and structurally characterized. These complexes have two different ligands with which the pendant amines of the diphosphine ligand can interact. The solid state structure of cis-Fe(PPh2NBn2)2Cl2 reveals that the six-membered rings adjacent to the P atoms are in a boat confirmation, resulting in close N•••P distances that suggests the P atoms have a greater affinity for the lone pair of electrons on the N atom than chloride ligands. Similarly, boat conformations are observed for both rings adjacent to the hydride ligands of trans-[HFe(PPh2NBn2)2(CH3CN)]+ and trans-HFe(PPh2NBn2)2Cl, resulting in short N•••H distances. Spectroscopic and computational studies of trans-[HFe(PPh2NBn2)2(CO)]+, trans-[HFe(PPh2NBn2)(PPh2NBn2H)(CO)]2+, and trans-[HFe(PPh2NBn2)2(H2)]+ indicate the complexes are more stable when the pendant amines in boat conformations are adjacent to the hydride ligand. These data suggest an attractor ordering of H- > CO > H2 > PR3 > Cl- ~ CH3CN. This work was supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated by Battelle for the U.S. DOE. Computations were performed using the Cascade supercomputer at the Environmental Molecular Sciences Laboratory, a National Scientific User Facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL.

Liao, Qian↗
DOE OSTI2025

Semiconductor‐Electrocatalyst Contacts: Theory, Experiment, and Applications to Solar Water Photoelectrolysis

The goal of the work supported by this program was to use new types of photoelectrochemical experiments, supported by simulation and theory, to develop an improved microscopic picture of electron transfer in combined semiconductor|catalyst|solution (sem|cat|sol) systems. An emphasis was placed on developing techniques which can directly characterize electronic interfacial phenomena without first assuming a junction model. We then aimed to illustrate the design principles that enhance interfacial processes and enable high-efficiency devices. Our work thus provides deep insight into the processes that, in general, use light to drive chemical reactions.

14 SOLAR ENERGY↗