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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
NASA NTRS1991

Optimum Platinum Loading In Pt/SnO2 CO-Oxidizing Catalysts

Platinum on tin oxide (Pt/SnO2) good catalyst for oxidation of carbon monoxide at or near room temperature. Catalytic activity peaks at about 17 weight percent Pt. Catalysts with platinum loadings as high as 46 percent fabricated by technique developed at Langley Research Center. Work conducted to determine optimum platinum loading for this type of catalyst. Major application is removal of unwanted CO and O2 in CO2 lasers.

Schryer, David R.↗
NASA NTRS2017

Development of Augmented Spark Impinging Igniter System for Methane Engines

The Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) program is establishing multiple no-funds-exchanged Space Act Agreement (SAA) partnerships with U.S. private sector entities. The purpose of this program is to encourage the development of robotic lunar landers that can be integrated with U.S. commercial launch capabilities to deliver payloads to the lunar surface. As part of the efforts in Lander Technologies, NASA Marshall Space Flight Center (MSFC) is developing liquid oxygen (LOX) and liquid methane (LCH4) engine technology to share with the Lunar CATALYST partners. Liquid oxygen and liquid methane propellants are attractive owing to their relatively high specific impulse for chemical propulsion systems, modest storage requirements, and adaptability to NASA's Journey to Mars plans. Methane has also been viewed as a possible propellant choice for lunar missions, owing to the performance benefits and as a technology development stepping stone to Martian missions. However, in the development of methane propulsion, methane ignition has historically been viewed as a high risk area in the development of such an engine. A great deal of work has been conducted in the past decade devoted to risk reduction in LOX/CH4 ignition. This paper will review and summarize the history and results of LOX/CH4 ignition programs conducted at NASA. More recently, a NASA-developed Augmented Spark Impinging (ASI) igniter body, which utilizes a conventional spark exciter system, is being tested with LOX/CH4 to help support internal and commercial engine development programs, such as those in Lunar CATALYST. One challenge with spark exciter systems, especially at altitude conditions, is the ignition lead that transmits the high voltage pulse from the exciter to the spark igniter (spark plug). The ignition lead can be prone to corona discharge, reducing the energy delivered by the spark and potentially causing non-ignition events. For the current work, a commercial compact exciter system, which eliminates this high voltage cabling, was tested at altitude conditions. A modified, conventional exciter system with an improved ignition lead was also recently tested at altitude conditions. This test program demonstrated the capability of these exciter systems to operate at altitude. While more extensive testing may be required, these systems or similar ones may be used for future NASA and commercial engine programs.

methane↗
DOE OSTI2024

A Reactor Scale-Up Methodology from Lab-Scale to Pilot-Scale Operations: Numerical Modeling of THFA Dehydration to DHP in Packed-Bed Reactors

This manuscript discusses developing a model-based scale-up methodology for a successful technology transfer of gas-phase catalytic reactors from a lab-scale to a pilot-scale operation. The manuscript demonstrates the methodology for gas-phase dehydration of tetrahydrofurfuryl alcohol (THFA) to dihydropyran (DHP) process over commercial Al 2 O 3 catalysts. A two-dimensional reactor model was developed using COMSOL Multiphysics 6.1 software. The model solves heat and mass transport equations in bed-scale and particle scales simultaneously. This powerful feature enables accurate prediction of the heat and mass transfer limitations in pilot-scale reactors, if any exists. Further, the model uses isothermal lab-scale experimental data to derive and validate the reaction chemistry, flow fields and boundary conditions. The model was then scaled-up to project conversion, selectivity, yield and formation rate of DHP in a pilot-scale reactor. The results highlight the complex nature of chemistry, heat, and mass transfer effects in lab-scale and pilot-scale reactors. The model results inform the possible operational limitations of the pilot-scale reactor and design strategies to improve process efficiency. Although the scale-up approach is explained through the THFA dehydration process, the methodology is applicable to any catalytic packed-bed reactor models for a successful process scale-up.

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

Substrate-Driven Catalyst Reducibility for Oxygen Evolution and Its Effect on the Operation of Proton Exchange Membrane Water Electrolyzers

To increase the efficiency of hydrogen production by proton exchange membrane water electrolyzers (PEMWEs), the relationships between the specific activity and stability of the membrane–electrode assembly (MEA) must be clarified. Ir oxide electrodeposited on Ti substrate is used as an oxygen electrode, and its electronic properties and electrochemical behavior in PEMWE operation are observed. The electrode, fabricated through a facile strategy based on annealing in the air atmosphere, enhances the specific oxygen evolution reaction (OER) activity and stability in PEMWE operation. Furthermore, the electronic catalyst–substrate interactions associated with different reducibilities in the heteroatom system are studied. The morphology, electronic properties, and chemical state of the oxygen electrode are investigated through X-ray spectroscopy, microscopy techniques, and computational analyses. Thermal treatment of the catalyst-coated substrate decreases the bulk oxidation state of Ir and increases the surface oxidation state. According to the electrochemical and physical behavior analyses of PEMWEs, the oxygen content in the Ir oxide structure, which defines the OER activity and its stability, is influenced by the crystalline structure and formation of a stable interface between the catalyst and substrate. The outcomes can facilitate the development of strategies for enhancing the performance of PEMWEs and designing rational MEAs.

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

In situ Formation of Platinum-Carbon Catalysts in Propane Dehydrogenation

The catalytic production of propylene via propane dehydrogenation (PDH) is a key reaction in the chemical industry. By combining operando transmission electron microscopy with density functional theory analysis, we show that the intercalation and ordering of carbon on Pt interstitials to form Pt-C solid solutions is relevant for increasing propylene production. More specifically, we found that at the point of enhanced propylene formation, the structure of platinum nanoparticles is transformed into a transient caesium chloride-type Pt-C polymorph. At more elevated temperatures, the zincblende and rock salt polymorphs seemingly coexist. When propylene production was highest, multiple crystal structures consisting of Pt and carbon were occasionally found to coexist in one individual nanoparticle, distorting the Pt lattice. Catalyst coking was detected at all stages of the reaction, but did initially not affect all particles. These findings could lead to the development of novel synthesis strategies towards tailoring highly efficient PDH catalysts.

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

Reconstruction of Thiospinel to Active Sites and Spin Channels for Water Oxidation

Water electrolysis is a promising technique for carbon neutral hydrogen production. A great challenge remains at developing robust and low-cost anode catalysts. Many pre-catalysts are found to undergo surface reconstruction to give high intrinsic activity in the oxygen evolution reaction (OER). The reconstructed oxyhydroxides on the surface are active species and most of them outperform directly synthesized oxyhydroxides. The reason for the high intrinsic activity remains to be explored. Here, a study is reported to showcase the unique reconstruction behaviors of a pre-catalyst, thiospinel CoFe 2 S 4 , and its reconstruction chemistry for a high OER activity. The reconstruction of CoFe 2 S 4 gives a mixture with both Fe–S component and active oxyhydroxide (Co(Fe)O x H y ) because Co is more inclined to reconstruct as oxyhydroxide, while the Fe is more stable in Fe–S component in a major form of Fe 3 S 4 . The interface spin channel is demonstrated in the reconstructed CoFe 2 S 4 , which optimizes the energetics of OER steps on Co(Fe)O x H y species and facilitates the spin sensitive electron transfer to reduce the kinetic barrier of O–O coupling. The advantage is also demonstrated in a membrane electrode assembly (MEA) electrolyzer. Finally, this work introduces the feasibility of engineering the reconstruction chemistry of the precatalyst for high performance and durable MEA electrolyzers.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Integrated Solar-Driven Device with a Front Surface Semitransparent Catalysts for Unassisted CO 2 Reduction

Monolithic integrated photovoltaic-driven electrochemical (PV-EC) artificial photosynthesis is reported for unassisted CO 2 reduction. The PV-EC structures employ triple junction photoelectrodes with a front mounted semitransparent catalyst layer as a photocathode. The catalyst layer is comprised of an array of microscale triangular metallic prisms that redirect incoming light toward open areas of the photoelectrode to reduce shadow losses. Full wave electromagnetic simulations of the prism array (PA) structure guide optimization of geometries and length scales. An integrated device is constructed with Ag catalyst prisms covering 35% of the surface area. The experimental device has close to 80% of the transmittance with a catalytic surface area equivalent 144% of the glass substrate area. Experimentally this photocathode demonstrates a direct solar-to-CO conversion efficiency of 5.9% with 50 h stability. Selective electrodeposition of Cu catalysts onto the surface of the Ag triangular prisms allows CO2 conversion to higher value products enabling demonstration of a solar-to-C 2+ product efficiency of 3.1%. This design featuring structures that have a semitransparent catalyst layer on a PV-EC cell is a general solution to light loss by shadowing for front surface mounted metal catalysts, and opens a route for the development of artificial photosynthesis based on this scalable design approach.

14 SOLAR ENERGY↗
DOE OSTI2019

In‐Situ Nanostructuring and Stabilization of Polycrystalline Copper by an Organic Salt Additive Promotes Electrocatalytic CO 2 Reduction to Ethylene

Abstract Bridging homogeneous molecular systems with heterogeneous catalysts is a promising approach for the development of new electrodes, combining the advantages of both approaches. In the context of CO 2 electroreduction, molecular enhancement of planar copper electrodes has enabled promising advancement towards high Faradaic efficiencies for multicarbon products. Besides, nanostructured copper electrodes have also demonstrated enhanced performance at comparatively low overpotentials. Herein, we report a novel and convenient method for nanostructuring copper electrodes using N , N ′‐ethylene‐phenanthrolinium dibromide as molecular additive. Selectivities up to 70 % for C ≥2 products are observed for more than 40 h without significant change in the surface morphology. Mechanistic studies reveal several roles for the organic additive, including: the formation of cube‐like nanostructures by corrosion of the copper surface, the stabilization of these nanostructures during electrocatalysis by formation of a protective organic layer, and the promotion of C ≥2 products.

Thevenon, Arnaud↗
DOE OSTI2024

Catalytically Active Site Mapping Realized through Energy Transfer Modeling

Abstract The demands of a sustainable chemical industry are a driving force for the development of heterogeneous catalytic platforms exhibiting facile catalyst recovery, recycling, and resilience to diverse reaction conditions. Homogeneous‐to‐heterogeneous catalyst transitions can be realized through the integration of efficient homogeneous catalysts within porous matrices. Herein, we offer a versatile approach to understanding how guest distribution and evolution impact the catalytic performance of heterogeneous host–guest catalytic platforms by implementing the resonance energy transfer (RET) concept using fluorescent model systems mimicking the steric constraints of targeted catalysts. Using the RET‐based methodology, we mapped condition‐dependent guest (re)distribution within a porous support on the example of modular matrices such as metal–organic frameworks (MOFs). Furthermore, we correlate RET results performed on the model systems with the catalytic performance of two MOF‐encapsulated catalysts used to promote CO 2 hydrogenation and ring‐closing metathesis. Guests are incorporated using aperture‐opening encapsulation, and catalyst redistribution is not observed under practical reaction conditions, showcasing a pathway to advance catalyst recyclability in the case of host–guest platforms. These studies represent the first generalizable approach for mapping the guest distribution in heterogeneous host–guest catalytic systems, providing a foundation for predicting and tailoring the performance of catalysts integrated into various porous supports.

Thompson, William J.↗
DOE OSTI2024

Catalytically Active Site Mapping Realized through Energy Transfer Modeling

Abstract The demands of a sustainable chemical industry are a driving force for the development of heterogeneous catalytic platforms exhibiting facile catalyst recovery, recycling, and resilience to diverse reaction conditions. Homogeneous‐to‐heterogeneous catalyst transitions can be realized through the integration of efficient homogeneous catalysts within porous matrices. Herein, we offer a versatile approach to understanding how guest distribution and evolution impact the catalytic performance of heterogeneous host–guest catalytic platforms by implementing the resonance energy transfer (RET) concept using fluorescent model systems mimicking the steric constraints of targeted catalysts. Using the RET‐based methodology, we mapped condition‐dependent guest (re)distribution within a porous support on the example of modular matrices such as metal–organic frameworks (MOFs). Furthermore, we correlate RET results performed on the model systems with the catalytic performance of two MOF‐encapsulated catalysts used to promote CO 2 hydrogenation and ring‐closing metathesis. Guests are incorporated using aperture‐opening encapsulation, and catalyst redistribution is not observed under practical reaction conditions, showcasing a pathway to advance catalyst recyclability in the case of host–guest platforms. These studies represent the first generalizable approach for mapping the guest distribution in heterogeneous host–guest catalytic systems, providing a foundation for predicting and tailoring the performance of catalysts integrated into various porous supports.

Thompson, William J.↗
DOE OSTI2023

Tuning the Interaction between Platinum Single Atoms and Ceria by Zirconia Doping for Efficient Catalytic Ammonia Oxidation

Aiming at the development of an efficient NH 3 oxidation catalyst to eliminate the harmful NH 3 slip from the stationary flue gas denitrification system and diesel exhaust aftertreatment system, a facile ZrO 2 doping strategy was proposed to construct Pt 1 /Ce x Zr 1–x O 2 catalysts with a tunable Pt-CeO 2 interaction strength and Pt–O–Ce coordination environment. According to the results of systematic characterizations, Pt species supported on Ce x Zr 1–x O 2 were mainly in the form of single atoms when x ≥ 0.7, and the strength of the Pt-CeO 2 interaction and the coordination number of Pt–O–Ce bond (CN Pt–O–Ce ) on Pt 1 /Ce x Zr 1–x O 2 showed a volcanic change as a function of the ZrO 2 doping amount. Here, it was proposed that the balance between the reasonable concentration of oxygen defects and limited surface Zr–O x species well accounted for the strongest Pt-CeO 2 interaction and the highest CN Pt–O–Ce on Pt/Ce 0.9 Zr 0.1 O 2 . It was observed that the Pt/Ce 0.9 Zr 0.1 O 2 catalyst exhibited much higher NH 3 oxidation activity than other Pt/Ce x Zr 1–x O 2 catalysts. The mechanism study revealed that the Pt 1 species with the stronger Pt-CeO 2 interaction and higher CN Pt–O–Ce within Pt/Ce 0.9 Zr 0.1 O 2 could better activate NH 3 adsorbed on Lewis acid sites to react with O 2 thus resulting in superior NH 3 oxidation activity. This work provides a new approach for designing highly efficient Pt/CeO 2 based catalysts for low-temperature NH 3 oxidation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Oxygen Atom Transfer as an Alternative Pathway for Oxygen–Oxygen Bond Formation

Fundamental understanding of catalytic mechanisms of water oxidation is a prerequisite for the design and development of efficient and rugged water oxidation catalysts. In this work, a detailed mechanistic study of the water oxidation mechanism of the [Ru II (npm)(4-pic) 2 (H 2 O)] 2+ (npm = 4-t-butyl-2,6-di(1',8'-naphthyrid-2'-yl)-pyridine, pic = 4-picoline) complex, [Ru II –OH 2 ] 2+ , reveals oxygen atom transfer from highly reactive ruthenium oxo intermediates to noncoordinating nitrogen atoms of the ligand as a novel route for oxygen evolution via storage of oxidizing equivalents as N-oxide groups on the ligand framework. Theoretical calculations show that the initial complex, [RuII–OH 2 ] 2+ , is transformed to a di-N-oxide [Ru II –OH 2 ,(-NO) 2 ] 2+ complex upon oxidation via facile OAT steps from Ru V =O species and that [Ru V =O,(-NO) 2 ] 3+ represents the most likely reactive species for the critical O–O bond formation. Furthermore, a new stepwise mechanism for oxygen evolution is introduced, which proceeds via coupling of Ru–O and N–O moieties producing a peroxide intermediate, [Ru V –OO–N,(-NO)] 3+ , and can compete with the water nucleophilic attack pathway for the oxygen evolution reaction. In this mechanism, a water molecule is oxidatively activated to an “oxygen atom” which is “stored” at a noncoordinating pyridine. Oxidative activation of a second water molecule, facilitated by coordination expansion of the intermediate N-oxide, generates the second oxygen atom required to produce a dioxygen molecule.

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

CO Reduction to Ethylene and Cyclopropane via a Trappable Ruthenium Methylidene

Ruthenium complexes based on cis-[Ru(bpy) 2 (CO) 2 ] 2+ (bpy is 2,2′-bipyridine) can reduce CO 2 and CO to C 1 products including methanol, but access to products containing C–C bonds has been elusive. A reaction pathway to convert CO into multicarbon products ethylene and cyclopropane is presented here, along with mechanistic studies elucidating the key intermediates in C–C bond formation. The ruthenium hydroxymethyl complex [Ru(bpy′) 2 (CO)(CH 2 OH)] + (bpy′ = 5,5′-dimethyl-2,2′-bipyridine) undergoes protonolysis to generate the ethylene complex [Ru(bpy′) 2 (CO)(C 2 H 4 )] 2+ even at −80 °C, with free ethylene released upon warming to room temperature. Experimental evidence implicates a highly electrophilic methylidene complex [Ru(bpy′) 2 (CO)(CH 2 )] 2+ as the key intermediate. The methylidene was successfully trapped with nitriles and pyridine, forming adducts (ylide complexes) that each have a unique reactivity profile. With an appropriate nitrile, the adduct can be characterized at low temperature before warming generates ethylene. A more stable pyridine adduct [Ru(bpy′) 2 (CO)(CH 2 pyridine)] 2+ was crystallographically characterized. Even ethylene itself is sufficiently nucleophilic to react with the electrophilic methylidene, revealing a route from CO to the C 3 hydrocarbon cyclopropane. Furthermore, the methods for controlling the reactivity of hydroxymethyl and methylidene complexes toward C–C bond formation can inform the development of CO and CO 2 reduction catalysts.

Carbene Compounds↗
DOE OSTI2022

On the mechanism of intermolecular nitrogen-atom transfer from a lattice-isolated diruthenium nitride intermediate

Catalyst confinement within microporous media provides the opportunity to site isolate reactive intermediates, enforce intermolecular functionalization chemistry by co-localizing reactive intermediates and substrates in molecular-scale interstices, and harness non-covalent host–guest interactions to achieve selectivities that are complementary to those accessible in solution. As part of an ongoing program to develop synthetically useful nitrogen-atom transfer (NAT) catalysts, we have demonstrated intermolecular benzylic amination of toluene at a Ru 2 nitride intermediate confined within the interstices of a Ru2-based metal–organic framework (MOF), Ru 3 (btc) 2 X 3 (btc = 1,3,5-benzenetricarboxylate, i.e., Ru-HKUST-1 for X = Cl). Nitride confinement within the extended MOF lattice enabled intermolecular C–H functionalization of benzylic C–H bonds in preference to nitride dimerization, which was encountered with soluble molecular analogues. Detailed study of the kinetic isotope effects (KIEs, i.e., k H /k D ) of C–H amination, assayed both as intramolecular effects using partially labeled toluene and as intermolecular effects using a mixture of per-labeled and unlabeled toluene, provided evidence for restricted substrate mobility on the time scale of interstitial NAT. Analysis of these KIEs as a function of material mesoporosity provided approximate experimental values for functionalization in the absence of mass transport barriers. Here, we disclose a combined experimental and computational investigation of the mechanism of NAT from a Ru 2 nitride to the C–H bond of toluene. Computed kinetic isotope effects for a H-atom abstraction (HAA)/radical rebound (RR) mechanism are in good agreement with experimental data obtained for C–H amination at the rapid diffusion limit. These results provide the first detailed analysis of the mechanism of intermolecular NAT to a C–H bond, bolster the use of KIEs as a probe of confinement effects on NAT within MOF lattices, and provide mechanistic insights unavailable by experiment because rate-determining mass transport obscured the underlying chemical kinetics.

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

Ultrathin ZSM-5 zeolite nanosheet laminated membrane for high-flux desalination of concentrated brines

The tremendous potential of zeolite membranes for efficient molecular separation via size-exclusion effects is highly desired by the energy and chemical industries, but its practical realization has been hindered by nonselective permeation through intercrystalline spaces and high resistance to intracrystalline diffusion in the conventional zeolite membranes of randomly oriented polycrystalline structures. Here, we report the synthesis of ZSM-5 zeolite nanosheets with very large aspect ratios and nanometer-scale thickness in the preferred straight channel direction. We used these ZSM-5 nanosheets to fabricate ultrathin (<500 nm) laminated membranes on macroporous alumina substrates by a simple dip-coating process and subsequent consolidation via vapor-phase crystallization. This ultrathin b -oriented ZSM-5 membrane has demonstrated extraordinary water flux combined with high salt rejection in pervaporation desalination for brines containing up to 24 weight % of dissolved NaCl. The ZSM-5 nanosheets may also offer opportunities to developing high-performance battery ion separators, catalysts, adsorbents, and thin-film sensors.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Direct Conversion of MnO2 into Atomic Mn Sites for Oxygen Reduction

Development of platinum group metal (PGM)-free catalysts has been investigated to replace the platinum group metal catalyst in future inexpensive polymer electrolyte membrane (PEM) fuel cells. Usually, synthetic methods for these PGM-free catalysts involve introducing transition-metal salts or molecules. Herein, we demonstrate a facile synthetic method to prepare PGM-free Mn-N-C catalysts by directly converting manganese oxides into highly active MnN4 sites. Typically, MnO2 is used as a Mn source. Ammonium chloride and benzimidazole are introduced during high-temperature treatment to enhance catalytic activity and stability further. Ammonia generated from the decomposition of ammonium chloride can improve the intrinsic ORR activity of MnNx moieties through chemical or electronic effects by introducing additional nitrogen groups. The Mn-N-C catalyst exhibits promising ORR activity, achieving a half-wave potential of 0.83 V in 0.5 M H2SO4, outperforming most PGM-free ORR catalysts. The robust carbon structure resulting from organic-molecule treatment is also verified by electrochemical and physical characterization, thereby improving the catalyst's durability.

Yang, Xiaoxuan↗