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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 1,423 records · Page 79
All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

Phosphoric acid fuel cell platinum use study

The U.S. Department of Energy is promoting the private development of phosphoric acid fuel cell (PAFC) power plants for terrestrial applications. Current PAFC technology utilizes platinum as catalysts in the power electrodes. The possible repercussions that the platinum demand of PAFC power plant commercialization will have on the worldwide supply and price of platinum from the outset of commercialization to the year 2000 are investigated. The platinum demand of PAFC commercialization is estimated by developing forecasts of platinum use per unit of generating capacity and penetration of PAFC power plants into the electric generation market. The ability of the platinum supply market to meet future demands is gauged by assessing the size of platinum reserves and the capability of platinum producers to extract, refine and market sufficient quantities of these reserves. The size and timing of platinum price shifts induced by the added demand of PAFC commercialization are investigated by several analytical methods. Estimates of these price shifts are then used to calculate the subsequent effects on PAFC power plant capital costs.

Lundblad, H. L.↗
NASA NTRS1999

Demonstration of an Ultra-Short Channel Metal Monolith Catalytic Reactor for Trace Contaminant Control Applications

The International Space Station (ISS) Trace Contaminant Control Subassembly (TCCS) design is based upon proven, highly reliable technology. However, because its core unit operations rely upon expendable activated charcoal and an indirectly heated high temperature catalyst, annual logistics mass, crew time, and power consumption requirements are significant. To address this situation, a unique catalytic reactor design has been developed which is suitable for retrofit into the TCCS's high temperature catalytic oxidizer (HTCO) assembly. The unique design, which employs a metallic, ultra-short channel length monolith (USCM) catalyst substrate, was tested in a flight-like TCCS HTCO assembly to investigate its performance characteristics. Test results indicate that retrofitting the TCCS with a USCM-based catalytic reactor is feasible and that it may provide significant reductions in logistics mass, crew time, and power consumption. Savings indicated by test results are up to 81% for annual logistics, 56% for crew time, and 77% for startup transient duration. In addition, its demonstrated ability to operate in a power saving mode provides up to a 43% savings in average power consumption. A summary of the USCM demonstration test objectives, approach, results, and specific benefits to the TCCS's process economics are presented,

Perry, J. L↗
DOE OSTI2017

Role of Surface Chemistry on Catalyst/Ionomer Interactions for Transition Metal–Nitrogen–Carbon Electrocatalysts

The role of the interaction between doped carbon-based materials and ionic conductors is essential in multiple technologies, from fuel cells and energy storage devices to conductive polymer composites. In this paper, we report how the surface chemistry of transition metal–nitrogen–carbon (MNC) electrocatalysts affects catalyst–ionomer interaction and the resulting structure of cathodes. The cathode structure resulting from these interactions is directly related to the performance in membrane electrode assembly (MEA) fuel cells. To advance the development of platinum group metal (PGM)-free electrodes for the oxygen reduction reaction it is necessary to understand the structure of the catalyst layers with focus on chemistry and distribution of active sites and ionomer morphology. To assess catalyst interaction with an ionomer, X-ray photoelectron spectroscopy is applied to study the chemistry of catalyst layers while density functional theory (DFT) is used to calculate adsorption energies of the ionomer side chain on different nitrogen species. We report that a high surface concentration of hydrogenated nitrogen at the surface of MNC catalysts causes inefficient ionomer morphology, while an abundance of surface oxides promotes both an efficient distribution of active sites and an optimal ionomer–catalyst interface. The critical role of protonation of nitrogen within catalytic layers in inhibiting proton transport during fuel cell operation is also suggested. As a result, this is the first report of the effect the surface chemistry of MNC catalysts, in the presence of the ionomer, has on the structure and performance of MEA electrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Performance of a Half-Heusler Thermoelectric Generator for Automotive Application

Thermoelectric generators (TEGs) have been researched and developed for harvesting energy from otherwise wasted heat. For automotive applications this will most likely involve using internal combustion engine exhaust as the heat source, with the TEG positioned after the catalyst system. Applications to exhaust gas recirculation systems and compressed air coolers have also been suggested. A thermoelectric generator based on half-Heusler thermoelectric materials was developed, engineered, and fabricated, targeting a gasoline passenger sedan application. This generator was installed on a gasoline engine exhaust system in a dynamometer cell, and positioned immediately downstream of the closecoupled three-way catalyst. The generator was characterized using a matrix of steady-state conditions representing the important portions of the engine map. Detailed performance results are presented. Measurements indicate the generator can produces over 300 W of power with 900 °C exhaust at relatively high flow rates, but less than 50 W when the exhaust is 600 °C and at lower flow rates. The latter condition is typical of standard test cycles and most driving scenarios.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2018

Simulation of the Dynamics of Isothermal Growth of Single-Layer Graphene on a Copper Catalyst in the Process of Chemical Vapor Deposition of Hydrocarbons

A new kinetic model of isothermal growth of single-layer graphene on a copper catalyst as a result of the chemical vapor deposition of hydrocarbons on it at a low pressure has been developed on the basis of in situ measurements of the growth of graphene in the process of its synthesis. This model defines the synthesis of graphene with regard for the chemisorption and catalytic decomposition of ethylene on the surface of a copper catalyst, the diffusion of carbon atoms in the radial direction to the nucleation centers within the thin melted near-surface copper layer, and the nucleation and autocatalytic growth of graphene domains. It is shown that the time dependence of the rate of growth of a graphene domain has a characteristic asymmetrical bell-like shape. The dependences of the surface area and size of a graphene domain and the rate of its growth on the time at different synthesis temperatures and ethylene concentrations have been obtained. Time characteristics of the growth of graphene domains depending on the parameters of their synthesis were calculated. The results obtained can be used for determining optimum regimes of synthesis of graphene in the process of chemical vapor deposition of hydrocarbons on different catalysts with a low solubility of carbon.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Efficient hydrogen storage and production using a catalyst with an imidazoline-based, proton-responsive ligand

A series of new imidazoline-based iridium complexes has been developed for hydrogenation of CO 2 and dehydrogenation of formic acid. One of the proton-responsive complexes bearing two –OH groups at ortho and para positions on a coordinating pyridine ring (3 b) can catalyze efficiently the chemical fixation of CO 2 and release H 2 under mild conditions in aqueous media without using organic additives/solvents. Notably, hydrogenation of CO 2 can be efficiently carried out under CO 2 and H 2 at atmospheric pressure in basic water by 3 b, achieving a turnover frequency of 106 h –1 and a turnover number of 7280 at 25 °C, which are higher than ever reported. Furthermore, highly efficient CO-free hydrogen production from formic acid in aqueous solution employing the same catalyst under mild conditions has been achieved, thus providing a promising potential H 2 -storage system in water.

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

Determining the Role of Synthesis and Reaction Conditions on the Exposed Surface and Shape of ..beta..-Mo2C Catalysts

The production of drop-in quality biofuels typically can be achieved through catalytic fast pyrolysis (CFP) of biomass, followed by hydrodeoxygenation (HDO) of the vapor-phase product to reduce the oxygen content and stabilize the bio-oil product. To favor selectivity toward desired deoxygenation products, bifunctional catalysts with both acidic and hydrogenation sites are often employed. Due to both its oxophilicity and its ability to promote hydrogenation reactions, molybdenum carbide catalysts have shown promise for promoting the HDO of CFP vapors. However, the surface structure and composition of carbide catalyst particles are not well understood, precluding the establishment of fundamental structure-function relationships needed for the rational development of molybdedum carbide for HDO, as well as other reactions. For orthorhombic ..beta..-Mo2C, the (100) facet is largely studied for computational surface-reaction analyses, possibly due to its similarities with the close-packed (111) facet of noble-metal catalysts. However, it has previously been postulated through ab initio thermodynamic studies that the (111), (110), and (011) facets are most stable, though there is no consensus. Furthermore, while a majority of previous surface stability analyses of ..beta..-Mo2C focus on bulk terminations, the highly carburizing synthesis conditions and the use of ..beta..-Mo2C in carbon-containing reaction applications could introduce non-stoichiometric coverages of surface carbon. As such, this study uses ab initio thermodynamics calculations to assess the relative surface stability of the low-index facets of ..beta..-Mo2C, including consideration of varying the coverage of surface carbon. From this information, Wulff constructions are utilized to predict the synthesis and reaction condition-dependent shape and surface carbon composition of ..beta..-Mo2C catalyst particles.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2019

Interfacial charge transfer in Pt-loaded TiO 2 P25 photocatalysts studied by in-situ diffuse reflectance FTIR spectroscopy of adsorbed CO

The efficiency of photocatalytic systems is strongly depending on the charge carrier transfer from the excited semiconductor to co-catalyst particles attached on its surface. In this study, we investigated the influence of photo-induced charge transfer in photoplatinized TiO 2 P25 photocatalysts by diffuse reflectance FTIR spectroscopy of CO molecules adsorbed on the Pt co-catalyst under well-defined gas phase conditions. In contrast to aqueous conditions, where shifts of the CO stretching vibration of up to 50 cm -1 have been reported, the observed shifts under gas phase conditions are very small (<1 cm -1 ). This demonstrates that the difference in dielectric properties between aqueous electrolytes and vacuum are critical for the development of prominent shifts of adsorbed CO bands upon trapping of photogenerated charge carriers on co-catalyst particles. The experimental findings are discussed in terms of an electrostatic Stark effect, charge screening, co-adsorption, coverage-dependent shifts of the vibrational bands of adsorbed CO and photocatalytic surface reactions.

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

Characterization of Porous Transport Layers Towards the Development of Efficient Proton Exchange Membrane Water Electrolysis

The current goals for implementing the hydrogen economy have highlighted a need to further optimize water-splitting technologies for clean hydrogen production. Proton exchange membrane water electrolysis (PEMWE) is a leading technology, but further optimizations of anode materials including the porous transport layer (PTL) and the adjacent catalyst layer (CL) are required to increase overall cell performance and reduce cost. This literature review describes advances in PTL development and characterization, highlighting early PTL characterization work and most common methods including capillary flow porometry and mercury intrusion porometry, optical imaging, neutron and x-ray radiography, and x-ray computed tomography. The article also discusses PTL protective coatings and their characterizations, focusing on platinum group metal (PGM)-based coatings, alternative non-PGM-based coatings, post-treated PTLs, and investigations into thin PGM-based coatings. Furthermore, it highlights the integration of the PTL and the adjacent CL along with associated characterization challenges. Lastly, this review discusses future developments in the characterization needed to improve PEMWE's performance and long-term durability are discussed.

08 HYDROGEN↗
DOE OSTI2020

Rapid microwave-assisted preparation of high-performance bifunctional Ni3Fe/Co-N-C for rechargeable Zn-air battery

Precious metal-free bifunctional catalysts offer scalable possibilities for achieving oxygen cathodes in rechargeable metal-air batteries. Literature thus far suggests that the oxygen reduction and evolution reactions (i.e ORR and OER) take place at different active sites. However, the design and preparation of oxygen electrocatalysts with high-performance is still a great challenge. This work develops a general approach to introduce a nanoparticle that offers oxygen evolution reaction sites onto an oxygen reduction reaction catalyst via rapid microwave treatment. The metal–organic frameworks (Co, ZIF-8) derived Co-N-C with high ORR performance is employed as a support to homogeneously disperse OER active Ni3Fe nanoparticles. Potentials of 1.54 V and 0.79 V have been achieved at current densities of 10 mA cm -2 for OER and 3 mA cm -2 toward ORR, respectively. The developed rechargeable Zn-air battery assembled with Ni 3 Fe/Co-N-C as an oxygen-electrode exhibits superior efficiency and robust durability, exceeding that of commercial Pt/C + IrO 2 . Furthermore, the satisfactory activity of our fabricated wristband shows the successfully practical application of flexible Zn-air batteries for wearable devices.

25 ENERGY STORAGE↗
NASA NTRS1972

Development of advanced fuel cell system

Weight, life and performance characteristics optimization of hydrogen-oxygen fuel cell power systems were considered. A promising gold alloy cathode catalyst was identified and tested in a cell for 5,000 hours. The compatibility characteristics of candidate polymer structural materials were measured after exposure to electrolyte and water vapor for 8,000 hours. Lightweight cell designs were prepared and fabrication techniques to produce them were developed. Testing demonstrated that predicted performance was achieved. Lightweight components for passive product water removal and evaporative cooling of cells were demonstrated. Systems studies identified fuel cell powerplant concepts for meeting the requirements of advanced spacecraft.

Grevstad, P. E.↗
DOE OSTI2023

Kinetic and X-ray Absorption Spectroscopic Analysis of Catalytic Redox Cycles over Highly Uniform Polymetal Oxo Clusters

Metal–organic framework materials (MOFs) offer an opportunity for investigating catalytic properties of polymetal oxo clusters that are highly well defined and uniform in nature, in contrast to other classes of catalysts that may exhibit a propensity toward active site heterogeneity. We report herein a kinetic and X-ray absorption spectroscopy (XAS) analysis of the two-electron oxidation of CO over divalent metal sites in MIL-100(M = Fe, Cr) (MIL = Materials of Institut Lavoisier) materials carrying μ 3 -oxo bridged trimers, and connect observations about the kinetic relevance of redox steps to density functional theory (DFT) predictions published previously. The high degree of uniformity evident from in situ titration measurements leads to a congruence in mechanistic inferences made from steady-state catalytic, transient stoichiometric, isotopic exchange, and isotopic tracer data that all point to a sequential mechanism comprised of separate oxidation and reduction half-cycle steps conjoined by an active oxygen intermediate. In situ XAS data reinforce mechanistic conclusions derived from kinetic analysis, and suggest that the active oxygen intermediate may be more appropriately characterized as an iron-oxyl (Fe 3+ –O – ) rather than an iron-oxo (Fe 4+ =O 2– ) species. The Cr analogue of MIL-100 exhibits contrasting rate features that can be rationalized using an identical sequence of steps as MIL-100(Fe), but with a highly dissimilar set of kinetic parameters that can also be validated using transient stoichiometric experiments. The larger coverages of active oxygen intermediates on MIL-100(Cr) are consistent with predictions from prior DFT studies that suggest more stable and less reactive active oxygen species for metals with lower d-electron counts, and point to metal identity as a lever for precisely controlling the kinetic relevance of oxidation and reduction half-cycles in catalytic redox sequences over polymetal oxo clusters. Importantly, the results presented point to the utility of developing broadly applicable structure–catalytic property relationships over MOF nodes specifically, and highly uniform catalysts more generally.

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

Heterogenization of Homogeneous Ruthenium(II) Catalysts for Carbon-Neutral Dehydrogenation of Polyalcohols

Liquid organic hydrogen carrier (LOHC) systems are an excellent alternative to pressurized gas and liquid hydrogen storage technologies due to their high volumetric storage capacities and straightforward adaptation to existing infrastructure. Homogeneous catalysts are promising for the selective and reversible release of hydrogen from LOHC. However, separation from product mixtures and recycling inhibit their use, particularly when comprised of costly low-abundance elements, motivating the development of heterogeneous versions that are more easily recovered and reused. Here, we describe two methods for the heterogenization of molecular Ru catalysts that efficiently dehydrogenate the polyalcohol LOHCs ethylene glycol (EG) and 1,2-propanediol (1,2-PDO). The heterogeneous versions of these catalysts maintain catalytic activity for hydrogen production comparable to the homogeneous complexes, with up to 81% conversion and 99% selectivity. Further, DFT modeling indicates mechanistic similarities for the dehydrogenations of EG and 1,2-PDO, with the rate-limiting steps associated with protonation of the Ru–H bond to form H 2 and the alkoxide species coordinated to Ru(II), followed by β-hydride elimination to regenerate the Ru–H bond. Overall, the data suggest these heterogenized molecular catalysts have potential for practical use in polyalcohol-based LOHC systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Series-Bosch Technology for Oxygen Recovery During Lunar or Martian Surface Missions

Long-duration surface missions to the Moon or Mars will require life support systems that maximize resource recovery to minimize resupply from Earth. To address this need, NASA previously proposed a Series-Bosch (S-Bosch) oxygen recovery system, based on the Bosch process, which can theoretically recover 100% of the oxygen from metabolic carbon dioxide. Bosch processes have the added benefits of the potential to recover oxygen from atmospheric carbon dioxide and the use of regolith materials as catalysts, thereby eliminating the need for catalyst resupply from Earth. In 2012, NASA completed an initial design for an S-Bosch development test stand that incorporates two catalytic reactors in series including a Reverse Water-Gas Shift (RWGS) Reactor and a Carbon Formation Reactor (CFR). In 2013, fabrication of system components, with the exception of a CFR, and assembly of the test stand was initiated. Stand-alone testing of the RWGS reactor was completed to compare performance with design models. Continued testing of Lunar and Martian regolith simulants provided sufficient data to design a CFR intended to utilize these materials as catalysts. Finally, a study was conducted to explore the possibility of producing bricks from spent regolith catalysts. The results of initial demonstration testing of the RWGS reactor, results of continued catalyst performance testing of regolith simulants, and results of brick material properties testing are reported. Additionally, design considerations for a regolith-based CFR are discussed.

Abney, Morgan B.↗
DOE OSTI2017

Developing a Thermodynamic Model for the Interactions between Water and Cu in the Zeolite SSZ-13

The Cu-exchanged zeolite SSZ-13 is an efficient catalyst in the selective catalytic reduction of nitrous oxides in the presence of ammonia, and understanding the nature of the active sites under realistic conditions is important in rationalizing its activity. Especially the interactions between Cu and water have drawn significant amounts of attention in recent years. In this work we develop a thermodynamic model for the water coordination of Cu based on static calculations and present occupational probabilities and phase diagrams for different Al distributions at different temperatures and water pressures. We find that only at high temperatures and low pressures is the bare Cu cation the most stable species and that the cation is solvated at lower temperatures and higher pressures. In the following we compare our results to experimental and theoretical work in this field and find good agreement. This work shows that it is possible to construct an accurate thermodynamic model for water interactions with Cu in zeolites and it will be interesting to see how a similar methodology can be applied to elucidate different problems in the future.

Göltl, Florian↗
DOE OSTI2017

Synthetic control and empirical prediction of redox potentials for Co 4 O 4 cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation

The oxo-cobalt cubane unit [Co 4 O 4 ] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co 4 O 4 ] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [Co III 4 O 4 ] 4+ /[Co III 3 Co IV O 4 ]5+ and [Co III 3 Co IV O 4 ] 5+ /[Co III 2 Co IV 2 O 4 ] 6+ redox potentials are reliably predicted by the pKas of the ligands. Hydrogen bonding is also shown to significantly raise the redox potentials, by ~500 mV. The potential-p K a correlation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure–reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts.

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

Translating Fundamental Insights into Ag-Based Bimetallic Electrocatalysts to Anion-Exchange Membrane Fuel Cells

To address challenges of high costs and scalability for fuel cells, it is essential to develop af-fordable and earth-abundant materials that are Pt-group-metal (PGM)-free. Recent advance-ments in PGM-free electrocatalysis for the oxygen reduction reaction (ORR) in alkaline media show that high catalyst loadings are needed to achieve high reaction rates; however, there are associated mass transport limitations. To address this issue, we develop low-loading ionomer-less Ag-bimetallic thin films by alloying with 3d block elements or Sn. We bridge knowledge from fundamental rotating disk electrode (RDE) studies to gas-diffusion cathodes in high-temperature anion-exchange membrane fuel cells (HT-AEMFCs), resulting in high-activity ORR catalysis and peak power densities up to 1.2 W cm-² geo for the Ag-Sn and Ag-Co alloys. Here, experimental post-characterization and theoretical calculations reveal small Co or Sn oxide nano-islands on Ag as likely active sites enhancing ORR activity, ultimately offering these low-loading PGM-free ORR materials as a viable path towards sustainable energy conversion.

Catalysts↗