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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 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
NASA NTRS2000

Catalyst Bed Instability Within the USFE H2O2/JP-8 Rocket Engine

Orbital Sciences Corporation has been awarded a contract by NASA's Marshall Space Flight Center, in cooperation with the U.S. Air Force Research Laboratory's Military Space Plane Technology Program Office, for the Upper Stage Flight Experiment (USFE) program. Orbital is designing, developing, and will flight test a new low-cost, 10,000 lbf hydrogen peroxide/ JP-8 pressure fed liquid rocket. During combustion chamber tests at NASA Stennis Space Center (SSC) of the USFE engine, the catalyst bed showed a low frequency instability occurring as the H202 flow reached about 1/3 its design rate. This paper reviews the USFE catalyst bed and combustion chamber and its operation, then discusses the dynamics of the instability. Next the paper describes the dynamic computer model used to recreate the instability. The model was correlated to the SSC test data, and used to investigate possible solutions to the problem. The combustion chamber configuration which solved the instability is shown, and the subsequent stable operation presented.

Johnson, Curtis W.↗
DOE OSTI2023

Depolymerization of polyesters by a binuclear catalyst for plastic recycling

Plastics play an essential role in modern society, however, the relentless growth of their production is threatening both human health and ecosystems. As a result, there are intensive efforts in developing recycling technologies to repurpose waste plastics into the building blocks for valuable materials. Here we show a binuclear complex that can catalyze the degradation of polyethylene terephthalate (PET)-the most widely used polyester globally-and a wide spectrum of other plastics including polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), polycaprolactone (PCL), polyurethane (PU) and Nylon 66. Inspired by hydrolases, the group of enzymes that catalyze bond cleavages with water, the present catalyst design features biomimetic Zn-Zn sites which activate the plastic, stabilize the key intermediate, and enable intramolecular hydrolysis. This synthetic catalyst delivers activities of 36 mg PET d -1 g catal -1 toward PET depolymerization at pH 8 and 40 oC, and of 577 g PET d -1 g catal -1 at pH 13 and 90 oC for scalable PET recycling. We further demonstrate the closed-loop production of a bottle-grade PET. This work presents a practical and viable solution to the sustainable management of plastics waste.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Electrochemical CO2 conversion to formic acid through the Andora Process

Electrochemical utilization or conversion of CO2 can be used to convert waste CO2 into targeted high-value and cost-effective commercial products. Conventional processes for CO2 conversion to fuel sources are challenging and expensive due to their requirement for high temperatures and pressures. Electrochemically, a catalyst can be used at a fixed applied potential to reduce CO2 to form a desired product with less competition at modest operating conditions. Formic acid (FA) has recently become a product of interest for CO2 conversion due to its potential for hydrogen storage and fuel cell applications. Electrochemically, FA is produced through a direct two-electron transfer process involving CO2 with a proton source, requiring less energy input and fewer reaction steps than traditional processes. However, there remain significant obstacles for the broader-scale implementation of CO2 on the market, including competition with unwanted CO and H, the presence of molecular oxygen, and stability of the electrocatalyst. In order to overcome some of these challenges, a new continuous flow Andora Process was developed consisting of two separate cells to decouple electrochemical reduction of the charge carrier with the FA production via an engineered catalyst. Recent experimental results show that with appropriate design changes and operating conditions to the flow system, FA production above 500 mM can be achieved along with efficiencies above 80%. TEA and LCA assessments of the Andora Process show a potential for the reduction in the GWP potential and cost saving compared to the current comparative formic acid production process.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Identifying Catalytic Active Sites of Trimolybdenum Phosphide (Mo 3 P) for Electrochemical Hydrogen Evolution

Solid-state electrocatalysis plays a crucial role in the development of renewable energy to reshape current and future energy needs. However, finding an inexpensive and highly active catalyst to replace precious metals remains a big challenge for this technology. Here, tri-molybdenum phosphide (Mo 3 P) is found as a promising nonprecious metal and earth-abundant candidate with outstanding catalytic properties that can be used for electrocatalytic processes. The catalytic performance of Mo3P nanoparticles is tested in the hydrogen evolution reaction (HER). The results indicate an onset potential of as low as 21 mV, H 2 formation rate, and exchange current density of 214.7 µmol s -1 g -1 cat (at only 100 mV overpotential) and 279.07 µA cm -2 , respectively, which are among the closest values yet observed to platinum. Combined atomic-scale characterizations and computational studies confirm that high density of molybdenum (Mo) active sites at the surface with superior intrinsic electronic properties are mainly responsible for the remarkable HER performance. The density functional theory calculation results also confirm that the exceptional performance of Mo 3 P is due to neutral Gibbs free energy (ΔG H* ) of the hydrogen (H) adsorption at above 1/2 monolayer (ML) coverage of the (110) surface, exceeding the performance of existing non-noble metal catalysts for HER.

Active sites↗
DOE OSTI2025

Integrated Ammonia Capture and Exchange on Ion‐Exchanged 4A Zeolites

Ammonia poses a challenge in effluent gas streams due to its corrosive nature. However, in fusion settings tritiated ammonia can be formed, leading to both tritium loss in inventory and the generation of reactive species. Therefore, identifying pathways in which both tritium can be recovered, and the ammonia can be easily handled would be beneficial. One such way to do so would be to combine two useful techniques: ammonia sequestration and hydrogen exchange (ND 3 →NH 3 ). However, materials that can both adsorb ammonia and subsequently perform reactions on ammonia have not been well explored. Here, in this work, we present the development of ion-exchanged A-type zeolites to be utilized as a support material for platinum catalysts. In this way, the zeolite can adsorb ammonia and the platinum catalyst can facilitate hydrogen exchange allowing for bifunctional reactivity of the material to be achieved. A variety of elements were explored for their effect on A-type zeolites and resulted in an isotopic difference in the adsorption of ND 3 and NH 3 , noting the use of deuterium as a surrogate for tritium. Several platinum-impregnated zeolites were able to remove ND 3 from the gas stream, indicating that utilizing these materials in isotope recovery processes would improve accountability of these valuable hydrogen isotopes.

Koch, Christopher J. [Savannah River National Labo↗
DOE OSTI2026

Insights into mixing of non-isothermal multi-polymer melts for complex plastics recycling

Catalytic recycling or upcycling of plastics is often limited not by catalyst performance, but by transport, arising from highly viscous, non-Newtonian polymer melts. In this work, we develop a reactor-scale framework that integrates rheological measurements, constitutive modeling, computational fluid dynamics (CFD), and experiments to quantify mixing, heat transfer, and dispersion in surrogate hydrocarbon melts representing mixed plastics systems. Temperature- and shear rate-dependent viscosity of low-density polyethylene (LDPE) and high-density polyethylene (HDPE) is measured to create two surrogate polymers (PLD and PHD) that capture the dominant shear-thinning flow behavior while neglecting strong elastic effects, enabling tractable simulation of non-isothermal, polymer-melt mixing using a Carreau-Arrhenius generalized Newtonian framework. Three-dimensional CFD simulations are employed to evaluate impeller performance in PLD using mixing time, cavern volume, thermal uniformity, and interfacial area for regimes in which viscoelastic effects are not dominant. We show that magnetic stir bars commonly used in lab-scale studies produce large thermal gradients (~60 °C) and poor mixing, even under idealized power delivery and polymer flow conditions. In contrast, close-clearance anchor impellers achieve near-isothermal operation, reduce mixing times by up to 5×, and provide >90% active circulation volume. We further demonstrate that, at low pseudo-Deborah number (De*), motor power requirements can be predicted directly from shear rate-dependent rheology using the Carreau-Arrhenius framework, enabling rational selection of operating conditions. Extension to surrogate immiscible multi-polymer systems based on PLD and PHD shows that interfacial area is highly sensitive to operating conditions and impeller design, with coaxial anchor-turbine configurations enhancing dispersion by up to 4 × .

Close-clearance impellers↗
DOE OSTI2022

An experimental and modeling study of the application of membrane contactor reactors to methanol synthesis using pure CO 2 feeds

We describe here a post-combustion CO 2 capture and utilization (CCU) technology that converts the CO 2 into methanol (MeOH), a valuable chemical, thus providing a way to monetize the carbon captured to offset process costs. Methanol synthesis (MeS) has been discussed recently for application to CCU, but thermodynamic limitations make it difficult to convert in a single pass a large CO 2 fraction. Conventional catalysts show slow kinetics in converting CO 2 -rich syngas (or pure CO 2 ) into MeOH. Our Group developed a novel MeS process, employing a membrane contactor reactor (MCR) system that attains carbon conversions significantly higher than equilibrium. Our focus here is to process pure CO 2 streams by combining the MCR with a separate reactor, which converts the CO 2 into a syngas via the reverse water gas shift (RWGS) reaction. In this preliminary effort, the RWGS reactor (RWGSR) is assumed to reach equilibrium. Additional MeS kinetic rate data are generated validating experimentally the ability of the MeS-MCR to process as a feed the RWGSR exit stream. The performance of the combined (RWGSR/MeS-MCR) system is then simulated using a recently developed MeS-MCR model. In conclusion, the findings are encouraging, and research is currently ongoing to experimentally validate the RWGSR/MeS-MCR system performance.

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

In-situ and in-operando analysis of voltage losses using sense wires for proton exchange membrane water electrolyzers

Proton exchange membrane water electrolyzer development requires understanding processes at the materials and interface levels to reach the required performance and lifetime targets for increasing market penetration. To achieve the required progress, it is critical to develop advanced in-situ diagnostics that allow observation of the changes that come with the reduction of catalyst loading combined with long-term intermittent operation. This work presents an internal voltage sensing method that enables observing internal voltage drops in an operating electrolyzer cell. It allows the total cell resistance to be separated into anode, CCM, and cathode resistance. The method is demonstrated by operating cells with different anode porous transport layers (PTLs). The changing properties of the PTLs result in significant variations of the resistances. Enhancing the PTL properties with a protective coating reduces the anode resistance significantly. In addition to these observations, the method enables a real-time monitoring of resistance related values that impact performance in water electrolyzers. Long-term experiments with the method allow us to gain insights into processes that occur during operation such as conditioning or degradation. The internal voltage sensing method presented in this study is a novel technique for diagnosing, analyzing, and optimizing water electrolyzers and other energy conversion devices.

42 ENGINEERING↗
DOE OSTI2017

Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions

Bio-oil produced from biomass fast pyrolysis often requires catalytic upgrading to remove oxygen and acidic species over zeolite catalysts. The elementary reactions in the mechanism for this process involve carbenium and oxonium ions. In order to develop a detailed kinetic model for the catalytic upgrading of biomass, rate constants are required for these elementary reactions. The parameters in the Arrhenius equation can be related to thermodynamic properties through structure-reactivity relationships, such as the Evans-Polanyi relationship. For this relationship, enthalpies of formation of each species are required, which can be reasonably estimated using group additivity. However, the literature previously lacked group additivity values for oxygenates, oxonium ions, and oxygen-containing carbenium ions. In this work, 71 group additivity values for these types of groups were regressed, 65 of which had not been reported previously and six of which were newly estimated based on regression in the context of the 65 new groups. Heats of formation based on atomization enthalpy calculations for a set of reference molecules and isodesmic reactions for a small set of larger species for which experimental data was available were used to demonstrate the accuracy of the Gaussian-4 quantum mechanical method in estimating enthalpies of formation for species involving the moieties of interest. Isodesmic reactions for a total of 195 species were constructed from the reference molecules to calculate enthalpies of formation that were used to regress the group additivity values. The results showed an average deviation of 1.95 kcal/mol between the values calculated from Gaussian-4 and isodesmic reactions versus those calculated from the group additivity values that were newly regressed. Importantly, the new groups enhance the database for group additivity values, especially those involving oxonium ions.

09 BIOMASS FUELS↗
DOE OSTI2020

Electron Affinity and Electronic Structure of Hexafluoroacetone (HFA) Revealed by Photodetaching the [HFA] •– Radical Anion

A great deal of effort has been focused on developing a metal-free catalytic system for epoxidation of unreactive alkenes. Fluoroketones are thought as remarkably promising catalysts for epoxidation reactions. The combination of fluorinated alcohols and catalytic amounts of hexafluoroacetone (HFA) gives a versatile and effective medium for epoxidation of various olefins with hydrogen peroxide. However, the fundamental physicochemical properties of HFA remained largely unclear, although they were very important to understand the related interactions. Here, in this study, we performed a joint study on the electron affinity and electronic structure of HFA employing negative ion photoelectron (NIPE) spectroscopy and quantum chemistry calculations. Two distinct bands with complicated vibrational progressions were observed in the 193 nm NIPE spectrum. The adiabatic/vertical detachment energies (ADE/VDE) were derived to be 1.42/2.06 and 4.43/4.86 eV for the ground singlet state and excited triplet state, respectively. Using the optimized geometries and vibrational frequencies of the anion and the neutral, the Franck–Condon factors were calculated for electron detachments to produce HFA in its lowest singlet and triplet states. Good agreements are obtained hereby for both bands between the experimental and calculated NIPE spectra, when taking into account combination vibrational excitations, unequivocally revealing that HFA possesses a singlet ground state with a giant singlet–triplet energy difference (ΔE ST ). The electron affinity (EA) and ΔE ST of HFA were therefore determined to be EA = 1.42 ± 0.02 eV and ΔE ST = −3.01 eV.

Wang, Lei↗
DOE OSTI2023

Controlling Mass Transport in Direct Carbon Dioxide Zero-Gap Electrolyzers via Cell Compression

The development of high-performance CO 2 electrolyzers is crucial for accelerating the sustainable production of fuels and chemicals integrated with renewable energy sources. Here, we introduce a methodology to actively control mass transport inside a realistic zero-gap membrane electrode assembly of a CO 2 electrolyzer by varying the gasket thickness, which consequently changes the cell compression. This allows control over the thickness and porosity of the gas diffusion electrodes, influencing the overall electrolyzer performance, as demonstrated using Ag-deposited electrodes. At low operating voltages (<2.9 V), both high- and low-compression electrolyzers exhibit similar faradaic efficiencies and partial current densities for CO formation. However, at high voltages, the low-compression electrolyzer with high electrode porosity demonstrates superior CO selectivity and activity with suppressed H 2 formation. These experimental results are validated by the computational membrane electrode assembly (MEA) model developed by using the measured in situ electrode thicknesses and electrode porosities. Additionally, liquid electrolyte saturation at the catalyst layer is found to play a dominant role in determining the mass transport, resulting in a decreased electrolyzer performance with low electrode porosity. Finally, the systematic investigation in this study improves the understanding of the transport dynamics in MEA-based devices and provides insights into optimizing device design parameters for industry-relevant CO 2 electrolysis.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Planar defect-driven electrocatalysis of CO 2 -to-C 2 H 4 conversion

The selectivity towards a specific C 2+ product, such as ethylene (C 2 H 4 ), is sensitive to the surface structure of copper (Cu) catalysts in carbon dioxide (CO 2 ) electro-reduction. The fundamental understanding of such sensitivity can guide the development of advanced electrocatalysts, although it remains challenging at the atomic level. In this work, we demonstrated that planar defects, such as stacking faults, could drive the electrocatalysis of CO 2 -to-C 2 H 4 conversion with higher selectivity and productivity than Cu(100) facets in the intermediate potential region (–0.50 ~ –0.65 V vs. RHE). The unique right bipyramidal Cu nanocrystals containing a combination of (100) facets and a set of parallel planar defects delivered 67% faradaic efficiency (FE) for C 2 H 4 and a partial current density of 217 mA cm –2 at –0.63 V vs. RHE. In contrast, Cu nanocubes with exclusive (100) facets exhibited only 46% FE for C 2 H 4 and a partial current density of 87 mA cm –2 at an identical potential. Both ex situ CO temperature-programmed desorption and in situ Raman spectroscopy analysis implied that the stronger *CO adsorption on planar defect sites facilitates CO generation kinetics, which contributes to a higher surface coverage of *CO and in turn an enhanced reaction rate of C–C coupling towards C 2+ products, especially C 2 H 4 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Editors’ Choice—Diffusion Media for Cation Contaminant Transport Suppression into Fuel Cell Electrodes

Polymer electrolyte membrane fuel cells provide an alternative option to fossil fuel-based energy conversion devices. However, the corrosion of fuel cell components, specifically the bipolar plates, introduces contaminants (e.g., Fe, Ni) into the membrane electrode assembly (MEA). These contaminants accelerate the ionomer degradation by acting as a Fenton’s reagent, decreasing the fuel cell’s durability. This study presents the mechanism and the diffusion media properties affecting the transport of cation contaminants into the MEA. Cation contaminant transport was studied after altering the gas diffusion layers (GDLs) wettability, emulating the GDL properties after prolonged operation, by ex situ hydrogen peroxide treatment or in situ electrochemical potential cycling. A GDL with crack-free microporous layer (MPL) showed a lower cation transport rate to the catalyst layer than MPL with cracks after both ex situ and in situ treatment. A novel GDL was developed from modification of the conventional GDL via the addition of a hydrophobic layer to the GDL substrate, which suppressed the contaminant cation transport significantly. This novel GDL also showed improved fuel cell performance.

25 ENERGY STORAGE↗
DOE OSTI2018

DEFE0023863 Final Report, Technology for GHG Emission Reduction and Cost-Competitive Mil-Spec Jet Fuel Production using CTL

Ceramatec Inc, in collaboration with IntraMicron (IM), the Energy & Environmental Research Center (EERC) and Sustainable Energy Solutions, LLC (SES), have completed a three-year research project integrating their respective proprietary technologies in key areas to demonstrate production of a jet fuel from coal and biomass sources. The project goals and objectives were to demonstrate technology capable of producing a “commercially-viable quantity” of jet fuel and make significant progress toward compliance with Section 526 of the Energy Independence and Security Act of 2007 (EISA 2007 §526) lifecycle greenhouse gas (GHG) emissions requirements. The Ceramatec led team completed the demonstration of nominal 2 bbl/day Fischer-Tropsch (FT) synthesis pilot plant design, capable of producing a nominal 1 bbl/day in the Jet-A/JP-8 fraction. This production rate would have a capacity of 1,000 gallons of jet fuel per month and provide the design basis of a 100 bbl/day module producing over 2,000 gallons of jet fuel per day. Co-gasification of coal-biomass blends enables a reduction of lifecycle greenhouse gas emissions from equivalent conventional petroleum derived fuel basis. Due to limits of biomass availability within an economic transportation range, implementation of a significant biomass feed fraction will require smaller plants than current world scale CTL and GTL FT plants. Hence a down-scaleable design is essential. The pilot plant design leverages Intramicron’s MicroFiber Entrapped Catalyst (MFEC) support which increases the catalyst bed thermal conductivity two orders of magnitude, allowing thermal management of the FT reaction exotherm in much larger reactor tubes. In this project, single tube reactors having 4.5 inch outer diameter and multi-tube reactors having 4 inch outer diameters were operated, with productivities as high as 1.5 gallons per day per linear foot of reactor tube. A significant reduction in tube count results from the use of large diameter reactor tubes, with an associated reduction in reactor cost. The pilot plant was designed with provisions for product collection capable of operating with conventional wax producing FT catalysts but was operated with a Chevron hybrid wax-free FT catalyst. Process simplification enabled by elimination of the wax hydrocracking process unit provides economic advantages in scaling to biomass capable plant sizes. Intramicron also provided a sulfur capture system based on their Oxidative Sulfur Removal (OSR) catalyst process. The integrated sulfur removal and FT systems were operated with syngas produced by the Transport Reactor Development Unit (TRDU) gasifier at the University of North Dakota EERC. SES performed modeling of their cryogenic carbon capture process on the energy, cost and CO2 emissions impact of the Coal-biomass synthetic fuel process.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

High-Temperature Alkaline Water Electrolysis

Hydrogen production for mobile and energy storage applications from water electrolysis is attractive due to its high efficiency, fast ramp rates, and potential for the clean energy economy. However, current hydrogen production from electrolysis comprises only a small fraction of the global hydrogen market due to the high cost associated with expensive stack materials (membrane, catalyst, and bipolar plates) and electricity consumption of the commercial electrolysis systems. In this project, we aimed to develop a high temperature alkaline water electrolyzer (HTAWE) that can simultaneously reduce the electrolyzer cost (by adopting cheap material) and improve energy efficiency (by enabling high-temperature operation).

08 HYDROGEN↗
NASA NTRS1973

Study of regenerable CO2 sorbents for extravehicular activity

Studies have shown that frequent extravehicular activities planned for future space missions will require regenerable life support systems. The oxides of magnesium, zinc, and silver were tested for their ability to react with CO2 to form the corresponding carbonates, and subsequent thermal regeneration to the oxides. Catalysts and binders were investigated to enhance CO2 sorption rates and structural integrity. A silver oxide formulation was developed which rapidly absorbs 95% of its theoretical capacity and has shown no degradation through 28 regenerations.

Colombo, G. V.↗
NASA NTRS1980

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

Alloy electrocatalysts on carbon supports were developed for hydrogen oxidation in the presence of carbon monoxide. These electrocatalysts match the best platinum on carbon catalysts for performance yet cost half as much. The results demonstrate that a significant reduction in anode electrocatalyst material cost can be achieved by replacing the platinum. Since surface characterization of this catalyst is important to explain its performance, several approaches and pitfalls to the elucidation of the surface characterization are presented.

Stonehart, P.↗