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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 1,063 records · Page 59

Development and Testing of a Methane/Oxygen Catalytic Microtube Ignition System for Rocket Propulsion

This study sought to develop a catalytic ignition advanced torch system with a unique catalyst microtube design that could serve as a low energy alternative or redundant system for the ignition of methane and oxygen rockets. Development and testing of iterations of hardware was carried out to create a system that could operate at altitude and produce a torch. A unique design was created that initiated ignition via the catalyst and then propagated into external staged ignition. This system was able to meet the goals of operating across a range of atmospheric and altitude conditions with power inputs on the order of 20 to 30 watts with chamber pressures and mass flow rates typical of comparable ignition systems for a 100 lbf engine.

Deans, Matthew↗

Development and Testing of a Methane/Oxygen Catalytic Microtube Ignition System for Rocket Propulsion

This study sought to develop a catalytic ignition advanced torch system with a unique catalyst microtube design that could serve as a low energy alternative or redundant system for the ignition of methane and oxygen rockets. Development and testing of iterations of hardware was carried out to create a system that could operate at altitude and produce a torch. A unique design was created that initiated ignition via the catalyst and then propagated into external staged ignition. This system was able to meet the goals of operating across a range of atmospheric and altitude conditions with power inputs on the order of 20 to 30 watts with chamber pressures and mass flow rates typical of comparable ignition systems for a 100 Ibf engine.

Deans, Matthew C.↗

Mapping of Heterogeneous Catalyst Degradation in Polymer Electrolyte Fuel Cells

Pt catalysts in polymer electrolyte fuel cells degrade heterogeneously as the catalyst particles are exposed to local variations throughout the catalyst layer during operation. State-of-the-art analytical techniques for studying degradation of Pt catalysts do not possess fine spatial resolution to elucidate such non-uniform degradation behavior at a large electrode level. A new methodology is developed to spatially resolve and quantify the heterogeneous Pt catalyst degradation over a large area (several cm ) of aged MEAs based on synchrotron X-ray microdiffraction. PEFC single cells are aged using voltage cycling as an accelerated stress test and the degradation heterogeneity at a micrometer length scale is visualized by mapping Pt catalyst particle size after voltage cycling. It is demonstrated in detail that the Pt catalyst particle size growth is non-uniform and follows the flow field geometry. The Pt particle size growth is greater in the area under the flow field land, while it is minimal in the area under the flow field channel. Additional non-uniformity is observed with the Pt particle size increasing more rapidly at the air outlet area than the Pt particle size at the inlet area.

36 MATERIALS SCIENCE↗

Operando Analyses of Solar Fuels Light Absorbers and Catalysts

Operando synchrotron radiation photoelectron spectroscopy in the tender X-ray energy range has been used to obtain information on the energy-band relations of semiconductor and metal-covered semiconductor surfaces while in direct contact with aqueous electrolytes under potentiostatic control. The system that was investigated consists of highly doped Si substrates that were conformally coated with ~70 nm titania films produced by atomic-layer deposition. TiO 2 /electrolyte and Si/TiO 2 /Ni/electrolyte interfaces were then analyzed by synchrotron radiation photoelectron spectroscopy. The PES data allows for determination of the flat-band position and identification of potential regions in which Fermi level pinning, depletion, or accumulation occurred. Operando X-ray absorption spectroscopy (XAS) techniques were additionally used to investigate the properties of heterogeneous electrocatalysts for the oxygen-evolution reaction. Operando XAS including the pre-edge, edge and EXAFS regions allowed the development of a detailed picture of the catalysts under operating conditions, and elucidated the changes in the physical and electronic structure of the catalyst that accompanied increases in the applied potential. Specifically, XAS data, combined with DFT studies, indicated that the activity of the electrocatalyst correlated with the formation of Fe dopant sites in γ-NiOOH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Final Report of a CRADA Between Pacific Northwest National Laboratory and Cummins, Incorporated (CRADA No.PNNL/283): “Enhanced High and Low Temperature Performance of NO x Reduction Catalyst Materials”

The NO x Storage-Reduction (NSR, also known as lean-NO x trap – LNT), is based upon the concept of storing NO x as nitrates over storage components, typically barium species, during a lean-burn operation cycle and then reducing the stored nitrates to N 2 during fuel-rich conditions over a precious metal catalyst [1]. NO x Selective Catalytic Reduction (SCR), on the other hand, is accomplished by deliberately introducing reductant urea into the engine exhaust to reduce NO x with the aid of a Cu(Fe)/zeolite catalyst [2]. These two technologies have been recognized as the most promising approaches for meeting stringent NO x emission standards for diesel vehicles within the Environmental Protection Agency’s (EPA’s) 2007/2010 mandated limits. For NSR, problems arising from either or both thermal and SO 2 deactivation must be addressed to meet durability standards. For SCR, SO 2 deactivation is less of an issue, but hydrothermal deactivation of the zeolite catalysts must be addressed. With continuing R&D efforts in advanced powertrains, highly novel operating modes for internal combustion engines (ICEs) are being researched in order to meet the very stringent new demands for fuel efficiency (e.g., U.S. ‘‘CAFE’’ standards for average miles/gallon are scheduled to increase dramatically over the next 10–15 years). These new ICE engine operation modes, while highly fuel-efficient, result in much lower exhaust temperatures than current engines; temperatures so low that it is hard to imagine how the current catalytic emission control technologies will be able to function. For example, while steady-state operation of the NO x reduction technology at 150 °C may be required, current ‘‘light-off’’ temperatures for CHA-based zeolite catalysts are closer to 200 °C. Therefore, understanding low-temperature limitations in NO x reduction has become one of the most daunting challenges in R&D on new catalyst materials and processes that can effectively eliminate emissions at these quite low exhaust temperatures. This project has two clear focuses: (1) development of potassium-based high-temperature NSR materials, and studying their key causes of deactivation and methods of regeneration. By comparing results obtained on ‘Simple Model’ Pt-K/Al 2 O 3 with ‘Enhanced Model’ Pt-K/ MgAlO x and Pt-K/TiO 2 materials, we have developed an understanding of the role of various additives on the deactivation and regeneration processes. Studies have also been performed on the real commercial samples being used in a Dodge Ram truck with a Cummins diesel emission control system. However, the results about these ‘commercial samples’ will not be covered in this report. Following a brief description of our experimental approach, we will present a few highlights from some of the work performed in this CRADA with more details about these results provided in publications/reports/presentations lists presented at the end of the report. (2) for the Cu and Fe/Chabazite SCR catalysts, since these are so newly developed and references from open literature and industry are nearly absent, our work started from zeolite synthesis and catalyst synthesis methodology development, before research on their low- and high-temperature performance, deactivation, regeneration, etc. was conducted. Again, most work reported here is based on our “model” catalysts synthesized in-house. Work done on the ‘commercial samples’ will not be covered in this report.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Membrane Electrode Assembly Manufacturing Automation Technology for the Electrochemical Compression of Hydrogen: Cooperative Research and Development (Final Report)

Electrochemical compression has the possibility to outcompete mechanical compression for hydrogen end- use applications. While HyET has a compressor that can output JO kilograms (kg)/day (fully scalable from home-to-industrial application) at up to 700 bar, the energy demand and reliability require top-quality electrochemical hydrogen compression (EHC) membrane electrode assemblies (MEAs), preferably prepared by cost-effective high-capacity manufacturing. High pressure requires a special MEA design, deviating from typical proton exchange membrane fuel cell (PEMFC) MEAs with adapted catalyst layer substrates, asking for a modified coating process. The National Renewable Energy Laboratory (NREL) will help HyET by developing an automated catalyst coating process fit for EHC MEA manufacturing. In addition, inline quality inspection methods will be developed/selected to improve the MBA quality as it is used for EHC stack assembly. In a joint effort, NREL and HyET will even design an automated manufacturing process for the EHC MEA and approach potential United States (US) suppliers of manufacturing equipment.

30 DIRECT ENERGY CONVERSION↗

Resolving Electrode Morphology’s Impact on Platinum Group Metal-Free Cathode Performance Using Nano-CT of 3D Hierarchical Pore and Ionomer Distribution

This paper reports on the characterization of polymer electrolyte fuel cell (PEFC) cathodes featuring a platinum group metal-free (PGM-free) catalyst using nano-scale resolution X-ray computed tomography (nano-CT) and morphological analysis. PGM-free PEFC cathodes have gained significant interest in the past decade since they have the potential to dramatically reduce PEFC costs by eliminating the large platinum (Pt) raw material cost. However, several challenges remain before they are commercially viable. Since these catalysts have lower volumetric activity, the PGM-free cathodes are thicker and are subject to increased gas and proton transport resistances that reduce the performance. To better understand the efficacy of the catalyst and improve electrode performance, a detailed understanding the correlation between electrode fabrication, morphology, and performance is crucial. In this work, the pore/solid structure and the ionomer distribution was resolved in three dimensions (3D) using nano-CT for three PGM-free electrodes of varying Nafion® loading. The associated transport properties were evaluated from pore/particlescale simulations within the nano-CT imaged structure. These characterizations are then used to elucidate the microstructural origins of the dramatic changes in fuel cell performance with varying Nafion® ionomer loading. We show that this is primarily a result of distinct changes in ionomer’s spatial distribution. The significant impact of electrode morphology on performance highlights the importance of PGM-free electrode development in concert with efforts to improve catalyst activity and durability.

42 ENGINEERING↗

Nitrogenated Graphene Quantum Dot-Derived Copper Single-Atom Catalyst for Oxygen Reduction Reaction

Despite the promise of fuel cells as sustainable energy conversion technologies, their widespread adoption is hindered by the high cost of platinum group metal (PGM) catalysts, particularly for catalyzing the oxygen reduction reaction (ORR) at the cathode. Here, we report copper-based single-atom catalysts (Cu-SACs) as cost-effective non-PGM alternatives for ORR. The catalysts were synthesized via simple pyrolysis of pyrene-derived amine-terminated graphene quantum dots (GQDs) in the presence of nitrogen and metal precursors. The abundant nitrogen functionality in GQDs effectively stabilized isolated Cu atoms during their conversion to porous carbon. A subsequent acid-washing step yielded a high density of atomically dispersed Cu active sites. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and high-resolution scanning transmission electron microscopy (HR-STEM) confirmed the effective incorporation of isolated Cu atoms into the carbon matrix through copper–nitrogen (Cu-N) coordination. Electrochemical measurements revealed excellent ORR activity with a dominant four-electron pathway. This synthetic strategy provides a practical route to developing economically viable, non-precious metal catalysts.

catalysts↗

Mechanistic study of a CO-free pathway in the methanol oxidation reaction over oxygen vacancies in NiOOH

The methanol oxidation reaction is a key reaction in direct methanol fuel cells. Prior research indicates that if oxygen vacancies in NiOOH serve as the active sites, the methanol oxidation mainly proceeds through the formate-involving pathway, which is a CO-free pathway, distinct from the conventional path over transition metal catalysts, though the fundamental reason for this suppressed CO formation is unclear. Herein, we report density functional theory calculations, through which we uncover the underlying reasons for this alternate path of methanol oxidation over the oxygen vacancies in NiOOH. We find that the existence of oxygen vacancies in NiOOH affects the adsorption configuration of adsorbates and that the interfacial charge transfer is minimal for CHO and CO intermediates. In addition, CHO, a key intermediate to form CO, adsorbs at the oxygen vacancy through the oxygen atom, leading to low stability due to the incomplete valence saturation of the carbon atom. This weak electronic interaction and instability effectively inhibit CHO formation and, consequently, CO formation. These insights provide valuable guidance for the development of efficient and CO-tolerant catalysts for methanol oxidation.

Ho, Thy [University of Oklahoma, Norman, OK (Unite↗

Oxygen electrodes for rechargeable alkaline fuel cells-II

The primary objective of this program is the investigation and development of electrocatalysts and supports for the positive electrode of moderate temperature single-unit rechargeable alkaline fuel cells. Approximately six support materials and five catalyst materials have been identified to date for further development.

Swette, L.↗

Oxygen electrodes for rechargeable alkaline fuel cells. II

The primary objective of this program is the investigation and development of electrocatalysts and supports for the positive electrode of moderate temperature, single-unit, rechargeable alkaline fuel cells. Approximately six support materials and five catalyst materials have been identified to date for further development.

Swette, L.↗

Sensitivity Analysis Tool for Electrochemical Conversion of CO 2 To CO: User Guide

This is the user guide for the tool described here: Development of technologies that convert carbon dioxide (CO 2 ) into products is part of the U.S. Department of Energy's Office of Fossil Energy and Carbon Management Carbon Conversion Program portfolio. One such technology under development converts CO 2 to value-added products via electrochemical reduction, where catalysts are used on the cathode to promote CO 2 conversion across the electrochemical catalyst (ECC) cell. Broadly, the ECC is integrated with balance of plant (BOP) equipment (e.g., compressors, pumps, heat exchangers, purification units) in system configurations to produce the desired product. To guide research and development (R&D) toward advancements that may make such conversion technologies economically competitive, researchers may use sensitivity analyses related to the ECC system cost and performance, including that of the cathodic and anodic catalysts. This tool is intended to inform developers and Program in assessing proposed R&D on ECC systems early in the development process. Results will guide researchers on where efforts would be best directed. The tool may be accessed here: https://www.netl.doe.gov/energy-analysis/details?id=55293cb1-6881-4181-a2b0-d00b711ce74b.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Straightforward Model for Quantifying Local pH Gradients Governing the Oxygen Evolution Reaction

The production and consumption of protons by an electrocatalyst will, under certain conditions, generate localized microenvironments with properties distinct from those of the bulk solution. These local properties are particularly impactful for reactions involving proton-coupled electron transfer, where the generation of locally basic or acidic environments may significantly influence the energy efficiency and reaction selectivity of the electrocatalyst. Whereas local pH environments have been observed and characterized in reductive half-reactions, including the CO 2 reduction and hydrogen evolution reactions, the incompatibility of conventional techniques and materials has limited studies in oxidative half-reactions, including the oxygen evolution reaction (OER), which provides the reducing equivalents for solar-to-fuels electrolysis. With the straightforward parameters bulk pH, buffer composition and pK a , and mass transport, we develop a model for describing local pH as a function of current density regardless of the microscopic details of the mechanism. Using an acid-stable PbO x OER catalyst, we observe the formation and dissipation of pH gradients during the OER and validate the model with voltammetric and potentiometric studies. Here, the model predicts how local acidic environments can develop over a narrow OER current density window, thus providing further motivation for the development of OER catalysts that are stable to acid, even when operating in basic aqueous conditions. More generally, the model is not restricted to the OER and is useful for determining the onset of local pH gradients for other electrocatalytic reactions that involve the consumption or generation of protons in energy conversion reactions.

Anions↗

Reusable Catalysts for Hydroformylation‐Based Reactions

Abstract Catalytic hydroformylation is an important reaction, widely studied by academics and applied in the chemical industry, and it is a paradigmatic example of a chemical reaction that is aligned with most of the Green Chemistry principles. In the last years, the global requirement for more sustainable chemical processes has boosted the development of more active, selective, and reusable hydroformylation catalysts. In this review, we highlight the most recent advances regarding the creation and expansion of reusable catalysts for hydroformylation and sequential processes that use hydroformylation as central reaction. The most relevant strategies for immobilization of hydroformylation catalysts are discussed, along with a critical analysis of their application in synthesis, based on catalytic activity, selectivity, and reusability.

Rodrigues, Fábio M. S.↗

Durable High-Power Membrane Electrode Assemblies with Low Pt Loading

Recent progress in developing and implementing Pt-alloy cathode catalysts and thin (10-15 micron) low resistance membranes has enabled high performance state of art (SOA) membrane electrode assembly (MEA) with low Pt loading. However, these high performing MEAs do not meet durability requirements, especially at peak power, because of complex degradation mechanisms that are sensitive to the materials, MEA design, and fuel cell operating strategy. Specifically, power degradation of the cathode occurs via Pt and Co dissolution as well as deterioration of O 2 transport properties. Additionally, thin membranes are subject to failure due to manufacturing defects in the adjacent gas diffusion media and electrodes and the formation of membrane-attacking radical species caused by high gas crossover. In this project led by General Motors LLC (GM), the objective was to enhance the durability of SOA MEA through optimization of operating conditions, instead of new materials development. Along with our project partners, we have mapped the impact of operating conditions on the durability of SOA MEA. Output of the project include a low Pt loading SOA MEA that exceeds Department of Energy (DOE) 2020 target of >1 W/cm 2 at rated power and pathway to achieve >5000 h of durability. Durability studies in the project provide a detailed understanding of failure modes and operating condition sensitivity on cathode and membrane failure, critical for defining operating conditions and hybridization strategies that can guide system controls to maximize low-Pt MEA life. The project also generated and validated degradation models that will provide future research direction, critical for guiding future cycles of automotive MEA development.

08 HYDROGEN↗

Coupling metal oxide nanoparticle catalysts for water oxidation to molecular light absorbers

Water oxidation, as a mandatory reaction of solar fuels conversion systems, requires the use of light absorbers with electronic properties that are well matched with those of the multi-electron catalyst in order to achieve high efficiency. Molecular light absorbers offer flexibility in fine tuning of orbital energetics, and metal oxide nanoparticles have emerged as robust oxygen evolving catalysts. These material choices offer a promising approach for the development of photocatalytic systems for water oxidation. However, efficient charge transfer coupling of molecular light absorbers and metal oxide nanoparticle catalysts has proven a challenge. Recent new approaches toward the efficient coupling of these components based on synthetic design improvements combined with direct spectroscopic observation and kinetic evaluation of charge transfer processes are discussed in this paper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Durability testing of advanced catalysts and catalyst supports for gas turbine engine combustors

The paper presents new information on the durability of a CATCOM catalyst operating at low-emission combustion temperatures (about 1527 K) with a liquid fuel, No. 2 diesel. Information on the activity of No. 2 diesel after 1000 hr of aging is given. In addition, a unique in situ activity test developed for monitoring the subtle changes in the catalyst activity of the CATCOM catalyst is also detailed. The study demonstrated the feasibility of using a CATCOM catalyst in catalytically supported thermal combustion for extended operating periods

Heck, R. M.↗

Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst

Platinum group metal–free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)–based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H 2 )–air fuel cell. We demonstrate H 2 -air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. In current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater than ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The catalytic active site we proposed, carbon-embedded nitrogen-coordinated iron (FeN 4 ), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗