Development of cathodic electrocatalysts for use in low temperature H2/O2 fuel cells with an alkaline electrolyte, January 1-31, 1966
Cathodic electrocatalyst development for use in low temperature hydrox fuel cell in alkaline electrolyte
CATALYST↗
SEARCH · Engineering Papers
Results for “catalyst development”
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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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.↗
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.↗
On-Board Chemical Propulsion Technology
On-board propulsion functions include orbit insertion, orbit maintenance, constellation maintenance, precision positioning, in-space maneuvering, de-orbiting, vehicle reaction control, planetary retro, and planetary descent/ascent. This paper discusses on-board chemical propulsion technology, including bipropellants, monopropellants, and micropropulsion. Bipropellant propulsion has focused on maximizing the performance of Earth storable propellants by using high-temperature, oxidation-resistant chamber materials. The performance of bipropellant systems can be increased further, by operating at elevated chamber pressures and/or using higher energy oxidizers. Both options present system level difficulties for spacecraft, however. Monopropellant research has focused on mixtures composed of an aqueous solution of hydroxl ammonium nitrate (HAN) and a fuel component. HAN-based monopropellants, unlike hydrazine, do not present a vapor hazard and do not require extraordinary procedures for storage, handling, and disposal. HAN-based monopropellants generically have higher densities and lower freezing points than the state-of-art hydrazine and can higher performance, depending on the formulation. High-performance HAN-based monopropellants, however, have aggressive, high-temperature combustion environments and require advances in catalyst materials or suitable non-catalytic ignition options. The objective of the micropropulsion technology area is to develop low-cost, high-utility propulsion systems for the range of miniature spacecraft and precision propulsion applications.
Reed, Brian D.↗
Assessment of Composite Delamination Self-Healing Via Micro-Encapsulation
Composite skin/stringer flange debond specimens manufactured from composite prepreg containing interleaf layers with a polymer based healing agent encapsulated in thin walled spheres were tested. As a crack develops and grows in the base polymer, the spheres fracture releasing the healing agent. The agent reacts with catalyst and polymerizes healing the crack. In addition, through-thickness reinforcement, in the form of pultruded carbon z-pins were included near the flange tips to improve the resistance to debonding. Specimens were manufactured with 14 plies in the skin and 10 plies in the stiffener flange. Three-point bend tests were performed to measure the skin/stiffener debonding strength and the recovered strength after healing. The first three tests performed indicated no healing following unloading and reloading. Micrographs showed that delaminations could migrate to the top of the interleaf layer due to the asymmetric loading, and hence, bypass most of the embedded capsules. For two subsequent tests, specimens were clamped in reverse bending before reloading. In one case, healing was observed as evidenced by healing agent that leaked to the specimen edge forming a visible "scar". The residual strength measured upon reloading was 96% of the original strength indicating healing had occurred. Hence, self-healing is possible in fiber reinforced composite material under controlled conditions, i.e., given enough time and contact with pressure on the crack surfaces. The micro-encapsulation technique may prove more robust when capsule sizes can be produced that are small enough to be embedded in the matrix resin without the need for using an interleaf layer. However, in either configuration, the amount of healing that can occur may be limited to the volume of healing agent available relative to the crack volume that must be filled.
O'Brien, T. Kevin↗
Biologically Inspired Purification and Dispersion of SWCNTs
A biologically inspired method has been developed for (1) separating single-wall carbon nanotubes (SWCNTs) from other materials (principally, amorphous carbon and metal catalysts) in raw production batches and (2) dispersing the SWCNTs as individual particles (in contradistinction to ropes and bundles) in suspension, as required for a number of applications. Prior methods of purification and dispersal of SWCNTs involve, variously, harsh physical processes (e.g., sonication) or harsh chemical processes (e.g., acid reflux). These processes do not completely remove the undesired materials and do not disperse bundles and ropes into individual suspended SWCNTs. Moreover, these processes cut long SWCNTs into shorter pieces, yielding typical nanotube lengths between 150 and 250 nm. In contrast, the present method does not involve harsh physical or chemical processes. The method involves the use of biologically derived dispersal agents (BDDAs) in an aqueous solution that is mechanically homogenized (but not sonicated) and centrifuged. The dense solid material remaining after centrifugation is resuspended by vortexing in distilled water, yielding an aqueous suspension of individual, separated SWCNTs having lengths from about 10 to about 15 microns.
Feeback, Daniel L.↗
Lander Technologies
Since 2006 NASA has been formulating robotic missions to the lunar surface through programs and projects like the Robotic Lunar Exploration Program, Lunar Precursor Robotic Program, and International Lunar Network. All of these were led by NASA Marshall Space Flight Center (MSFC). Due to funding shortfalls, the lunar missions associated with these efforts, the designs, were not completed. From 2010 to 2013, the Robotic Lunar Lander Development Activity was funded by the Science Mission Directorate (SMD) to develop technologies that would enable and enhance robotic lunar surface missions at lower costs. In 2013, a requirements-driven, low-cost robotic lunar lander concept was developed for the Resource Prospector Mission. Beginning in 2014, The Advanced Exploration Systems funded the lander team and established the MSFC, Johnson Space Center, Applied Physics Laboratory, and the Jet Propulsion Laboratory team with MSFC leading the project. The lander concept to place a 300-kg rover on the lunar surface has been described in the New Technology Report Case Number MFS-33238-1. A low-cost lander concept for placing a robotic payload on the lunar surface is shown in figures 1 and 2. The NASA lander team has developed several lander concepts using common hardware and software to allow the lander to be configured for a specific mission need. In addition, the team began to transition lander expertise to United States (U.S.) industry to encourage the commercialization of space, specifically the lunar surface. The Lunar Cargo Transportation and Landing by Soft Touchdown (CATALYST) initiative was started and the NASA lander team listed above is partnering with three competitively selected U.S. companies (Astrobotic, Masten Space Systems, and Moon Express) to develop, test, and operate their lunar landers.
Chavers, Greg↗
Leading University Students to the Edge of Space
For over 16 years, the Louisiana Space Grant Consortium (LaSPACE), the NASA Balloon Program Office (BPO), and the NASA Columbia Scientific Balloon Facility (CSBF) have collaborated in a series of high altitude balloon-based programs involving hands-on authentic learning experiences that expose university students and other participants to technical skills, teamwork dynamics, and effective communication methods. Such programs go beyond what is possible to achieve in a normal classroom and help prepare future engineers and scientists for a successful aerospace workforce career. In our collaborative effort, LaSPACE has focused on the program content and student mentoring while NASA BPO and CSBF provide balloon flight support and operations. The entry-level Louisiana Aerospace Catalyst Experiences for Students (LaACES) builds students’ skills in basic electronics, sensor interfacing, real-time programming, mechanical development, and project management. These skills are then applied to the design, development, fabrication, and flight of a small (∼500 gram) balloon payload. Finally, the payloads are flight-tested to an altitude of ∼30 km using a 2 kg latex sounding balloon. The LaACES program includes a set of lectures, activities, and Arduino Mega based electronic kits that are used for skill building and as a core control system for the student payload. The more advanced High Altitude Student Platform (HASP) is designed to carry ∼twelve 3 to 20 kg student payloads to an altitude of about 36 kilometers with flight durations of 10 to 20 hours using a ∼311,500 cubic meter, zero pressure balloon. HASP provides all student payloads with power, downlink telemetry, uplink commanding, and real-time HD video for instrument control and assessment during the flight. While originally developed for university students, these programs have been adapted to projects focused on high school teachers as well as affecting minorities underrepresented in aerospace related science and engineering fields. We are now in the process of adapting the LaACES materials to a pre-engineering curriculum for high school students as well as for widespread access over the internet. During this presentation, we will provide details of both the LaACES and HASP programs, how these programs have engaged participants from all demographic groups, and our current plans for continuing and expanding upon our success.
University↗
Atomic-resolution imaging as a mechanistic tool for studying single-site heterogeneous catalysis
Heterogeneous catalysts dominate the chemical industry but typically feature diverse, incompletely defined active sites. Thus, describing structure-activity relationships, unlike homogeneous catalysts, remains challenging. In contrast, molecularly defined single-site heterogeneous catalysts (SSHCs), using appropriate tools, are poised to address these challenges and provide new avenues for catalysis research and development. The present study explores eco-friendly H 2 production mediated by discrete MoO 2 sites supported on carbon nanohorns (CNHs) and active for alcohol dehydrogenation. While informative, detailed ensemble EXAFS/XANES/XPS, kinetic measurements, and DFT analysis alone cannot provide a full molecular picture of the reaction pathway. Here, using single-molecule atomic-resolution time-resolved electron microscopy (SMART-EM), we propose the identification of four key catalytic intermediates anchored to CNHs and uncover a new reaction pathway involving alkoxide/hemiacetal equilibration and acetal oligomerization. Furthermore, these intermediates are inferred through a combination of theory and SMART-EM, showcasing the potential of SMART-EM as a complementary tool for exploring mechanistic hypotheses in catalysis.
36 MATERIALS SCIENCE↗
Synthetic biodegradable polyhydroxyalkanoates (PHAs): Recent advances and future challenges
This article reviews the advances made over the past five decades of research in developing effective chemocatalytic pathways to synthesize polyhydroxyalkanoates (PHAs), a prominent class of biodegradable polyesters found in nature and considered as sustainable alternatives to petroleum-based non-degradable plastics. Focused in this review are recent efforts that seek to address the key challenges facing the biosynthetic routes by taking advantage of precision in synthesis, expedient tunability in polymer stereomicrostructures and structures of monomers and molecular catalysts, as well as scalability and speed in polymer production that chemical catalysis can offer. This article is organized by poly(3-hydroxybutyrate) (P3HB) stereomicrostructures (tacticities), from isotactic to syndiotactic to atactic P3HB materials, followed by other PHA homopolymers and copolymers. Under each type of stereochemically defined PHAs, monomers, catalysts, and polymerizations employed for the synthesis, as well as mechanistic aspects when possible, are described. Next, recent advances in expanding the PHA scope and developing functionalized, uncommon or unnatural PHAs, inaccessible by biological methods, especially block and stereoblock or stereosequenced PHAs, are highlighted in their synthetic methods and advanced materials properties. As a result, four key remaining challenges, and thus corresponding future directions directed at addressing those challenges, are discussed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Development of High Power Density Metal‐Supported Solid Oxide Fuel Cells
Abstract Symmetric‐structure metal‐supported solid oxide fuel cells (MS‐SOFCs) are fabricated by infiltrating catalysts on both anode and cathode side. Various aspects of the infiltration process are optimized. Performance is found to be sensitive to precursor dilution, catalyst loading, and catalyst calcining temperature. For an optimized cell with lanthanum strontium manganite (LSM) as cathode and Sm 0.2 Ce 0.8 O 2− δ mixed with Ni (SDCN) as anode, peak power densities of 0.44, 1.1, and 1.9 W cm −2 are achieved at 600, 700, and 800 °C, respectively. A fully symmetric MS‐SOFC with SDCN as both the anode and cathode sides achieves moderate peak power densities of 0.12, 0.37, and 0.76 W cm −2 at 600, 700, and 800 °C, respectively. A solvent‐based infiltration technique is also explored and found to be more effective than capillary forces alone but not as effective as vacuum infiltration.
Tucker, Michael C.↗
Protective Catalyst Systems on III-V and Si-based Semiconductors for Efficient, Durable Photoelectrochemical Water Splitting Devices
The overall goal of this project was to develop unassisted water splitting devices based on III-V materials, creating pathways to improve performance in terms of efficiency, improve durability, and cost. One major objective is to develop pathways to systems that can ultimately achieve > 20% solar-to-hydrogen (STH) efficiency. Another objective was to develop pathways to high efficiency systems that can operate on-sun for at least 2 weeks. With respect to cost, this research provide new approaches to tandem photoelectrode design and fabrication that one day may allow for costs to reach $200/m 2 . Two distinct water splitting schemes were explored: Scheme 1 aims to develop high efficiency devices with tandem III-V photoabsorbers (e.g. GaInP 2 /GaInAs) with Scheme 2 targeting cost reduction while maintaining high efficiency by growing InGaN on crystalline Si (InGaN/Si). Both schemes were employed to couple with thin film, semi-transparent, catalytic/protection layers containing reduced or zero precious metal content that can enhance durability while maintaining high efficiency and enabling low material costs. Overall the project greatly advanced the technology to developing high performance systems with increased durability, as demonstrated by true on-sun testing through partnership with the National Renewable Energy Laboratory (NREL).
08 HYDROGEN↗
Modeling the impact of structure and coverage on the reactivity of realistic heterogeneous catalysts
Adsorbates often cover the surfaces of catalysts densely as they carry out reactions, dynamically altering their structure and reactivity. Understanding adsorbate-induced phenomena and harnessing them in our broader quest for improved catalysts is a substantial challenge that is only beginning to be addressed. Here, in this work, we chart a path toward a deeper understanding of such phenomena by focusing on emerging in silico modeling methodologies, which will increasingly incorporate machine learning techniques. We first examine how adsorption on catalyst surfaces can lead to local and even global structural changes spanning entire nanoparticles, and how this affects their reactivity. We then evaluate current efforts and the remaining challenges in developing robust and predictive simulations for modeling such behavior. Last, we provide our perspectives in four critical areas—integration of artificial intelligence, building robust catalysis informatics infrastructure, synergism with experimental characterization, and adaptive modeling frameworks—that we believe can help surmount the remaining challenges in rationally designing catalysts in light of these complex phenomena.
catalytic mechanisms↗
Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides
Oxygen electrocatalysis plays a critical role in the efficiency of important energy conversion and storage systems. While many efforts have focused on designing efficient electrocatalysts for these processes, optimal catalysts that are inexpensive, active, selective, and stable are still being searched. Nonstoichiometric, mixed-metal oxides present a promising group of electrocatalysts for these processes due to the versatility of the surface composition and fast oxygen conducting properties. Herein, we demonstrate, using a combination of theoretical and experimental studies, the ability to develop design principles that can be used to engineer oxygen electrocatalysis activity of layered, mixed ionic-electronic conducting Ruddlesden– Popper (R–P) oxides. We show that a density function theory (DFT) derived descriptor, O 2 binding energy on a surface oxygen vacancy, can be effective in identifying efficient R–P oxide structures for oxygen reduction reaction (ORR). Using a controlled synthesis method, well-defined nanostructures of R–P oxides are obtained, which along with thermochemical and electrochemical activity studies are used to validate the design principles. This has led to the identification of a highly active ORR electrocatalyst, nanostructured Co-doped lanthanum nickelate oxide, which when incorporated in solid oxide fuel cell cathodes significantly enhances the performance at intermediate temperatures (~550 °C), while maintaining long-term stability. Here, the reported findings demonstrate the effectiveness of the developed design principles to engineer mixed ionic-electronic conducting oxides for efficient oxygen electrocatalysis, and the potential of nanostructured Co-doped lanthanum nickelate oxides as promising catalysts for oxygen electrocatalysis.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cobalt‐Doped Bismuth Nanosheet Catalyst for Enhanced Electrochemical CO 2 Reduction to Electrolyte‐Free Formic Acid
Electrochemical carbon dioxide (CO 2 ) reduction reaction (CO 2 RR) to valuable liquid fuels, such as formic acid/formate (HCOOH/HCOO − ) is a promising strategy for carbon neutrality. Enhancing CO 2 RR activity while retaining high selectivity is critical for commercialization. To address this, we developed metal-doped bismuth (Bi) nanosheets via a facile hydrolysis method. These doped nanosheets efficiently generated high-purity HCOOH using a porous solid electrolyte (PSE) layer. Among the evaluated metal-doped Bi catalysts, Co-doped Bi demonstrated improved CO 2 RR performance compared to pristine Bi, achieving ~90 % HCOO − selectivity and boosted activity with a low overpotential of ~1.0 V at a current density of 200 mA cm −2 . In a solid electrolyte reactor, Co-doped Bi maintained HCOOH Faradaic efficiency of ~72 % after a 100-hour operation under a current density of 100 mA cm −2 , generating 0.1 M HCOOH at 3.2 V. Density functional theory (DFT) results revealed that Co-doped Bi required a lower applied potential for HCOOH generation from CO 2 , due to stronger binding energy to the key intermediates OCHO* compared to pure Bi. In conclusion, this study shows that metal doping in Bi nanosheets modifies the chemical composition, element distribution, and morphology, improving CO 2 RR catalytic activity performance by tuning surface adsorption affinity and reactivity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Computational design of CO-tolerant Pt 3 M anode electrocatalysts for proton-exchange membrane fuel cells
CO is a typical contaminant in hydrogen fuel produced via steam reforming. Development of a CO-tolerant Pt-based anode for the proton-exchange membrane fuel cells (PEMFC) is of great interest to avoid catalyst deactivation caused by strong CO adsorption on Pt. Pt–Ru, Pt–Mo, and Pt 3 Sn are three known Pt-based bimetallic CO-tolerant anode materials. The enhanced CO-tolerance of these alloys has been generally attributed to a bifunctional effect enabling oxidative CO removal at low applied potential and a ligand effect between the two metals which weakens CO bonding and reduces CO surface coverage. In this study, we use density functional theory to calculate surface adsorption states under reaction conditions for Pt-based alloys. Our calculations provide a molecular-level understanding of the enhanced CO-tolerance of Pt alloys induced by the second metal. We find that Mo and Sn dopants promote CO-tolerance by reducing CO surface coverage and enabling CO oxidative removal at low applied potential. In contrast, Ru is not able to promote CO electro-oxidation at the low applied potential of the operating conditions of a PEMFC anode. The CO-tolerance induced by Ru is attributed to the reduction of CO coverage on Pt sites. Based on these mechanisms, we carried out a computational screening of Pt 3 M electrocatalysts for CO-tolerant PEMFC anodes. A number of promising candidates have been identified for experimental examination.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
3D Photocatalytic media for decontamination of water from pesticides
Highlights: • Development of new photocatalytic media for decontamination of water from pollutants. • Deposition of TiO{sub 2} on alveolar macroporous media using the sol-gel method. • Use of aluminum foam as photocatalyst support. • A complete degradation of pyrimethanil was observed using the developed media. - Abstract: This work focuses on the development of innovative photocatalytic material, for decontamination of water from pollutants, by functionalization of reticulated metallic foam with TiO{sub 2}. The composition and texture of the prepared photocatalyst support were characterized using scanning electron microscope. The results showed a good deposition of the catalyst on the surface of the tested media with a recovery rate of 40 ± 3% which was interesting comparing to the coating rate obtained with industrial media (<20%). To prove the efficiency of the developed materiel, the photodegradation of pyrimethanil, at room temperature using the developed support under UV radiation was tested. A complete degradation of pyrimethanil was observed. The time required for total elimination of the pesticide varies depending on the initial concentration and in general, it was observed that a higher pesticide concentration required a longer time to be eliminated, however, for all tested concentrations, 5 h were sufficient for total elimination.
36 MATERIALS SCIENCE↗
Using X-ray free-electron lasers for spectroscopy of molecular catalysts and metalloenzymes
The metal centers in metalloenzymes and molecular catalysts are responsible for the rearrangement of atoms and electrons during complex chemical reactions, and they enable selective pathways of charge and spin transfer, bond breaking/making and the formation of new molecules. Mapping the electronic structural changes at the metal sites during the reactions gives a unique mechanistic insight that has been difficult to obtain to date. The development of X-ray free-electron lasers (XFELs) enables powerful new probes of electronic structure dynamics to advance our understanding of metalloenzymes. The ultrashort, intense and tunable XFEL pulses enable X-ray spectroscopic studies of metalloenzymes, molecular catalysts and chemical reactions, under functional conditions and in real time. In this Technical Review, we describe the current state of the art of X-ray spectroscopy studies at XFELs and highlight some new techniques currently under development. With more XFEL facilities starting operation and more in the planning or construction phase, new capabilities are expected, including high repetition rate, better XFEL pulse control and advanced instrumentation. For the first time, it will be possible to make real-time molecular movies of metalloenzymes and catalysts in solution, while chemical reactions are taking place.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗