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At least 163 records · Page 9

Construction of Lattice Strain in Bimetallic Nanostructures and Its Effectiveness in Electrochemical Applications

Bimetallic nanocrystals (NCs), associated with various surface functions such as ligand effect, ensemble effect, and strain effect, exhibit superior electrocatalytic properties. The stress-induced surface strain effect can alter binding strength between the surface active sites and reactants as well as their intermediates, and the electrochemical performance of bimetallic NCs can be significantly facilitated by the lattice-strain modification via their morphologies, sizes, shell-thickness, surface defectiveness as well as compositions. Here in this review, an overview of fundamental principles, characterization techniques, and quantitative determination of the surface lattice strain is provided. Various strategies and synthesis efforts on creating lattice-strain-engineered bimetallic NCs, including the de-alloying process, atomic layer-by-layer deposition, thermal treatment evolution, one-pot synthesis, and other efforts are also discussed. It is further outlined how the lattice strain effect promotes electrochemical catalysis through the selected case studies. The reactions on oxygen reduction reaction, small molecular oxidation, water splitting reaction, and electrochemical carbon dioxide reduction reactions are focused. In particular, studies of lattice strain arisen from core–shell nanostructure and defectiveness are highlighted. Lastly, the potential challenges are summarized and the prospects of lattice-strain-based engineering on bimetallic nanocatalysts with suggestion and guidance of the future electrocatalyst design are envisioned.

36 MATERIALS SCIENCE↗

Physical/chemical closed-loop water-recycling

Water needs, water sources, and means for recycling water are examined in terms appropriate to the water quality requirements of a small crew and spacecraft intended for long duration exploration missions. Inorganic, organic, and biological hazards are estimated for waste water sources. Sensitivities to these hazards for human uses are estimated. The water recycling processes considered are humidity condensation, carbon dioxide reduction, waste oxidation, distillation, reverse osmosis, pervaporation, electrodialysis, ion exchange, carbon sorption, and electrochemical oxidation. Limitations and applications of these processes are evaluated in terms of water quality objectives. Computerized simulation of some of these chemical processes is examined. Recommendations are made for development of new water recycling technology and improvement of existing technology for near term application to life support systems for humans in space. The technological developments are equally applicable to water needs on Earth, in regions where extensive water recycling is needed or where advanced water treatment is essential to meet EPA health standards.

Herrmann, Cal C.↗

Physical/chemical closed-loop water-recycling for long-duration missions

Water needs, water sources, and means for recycling water are examined in terms appropriate to the water quality requirements of a small crew and spacecraft intended for long duration exploration missions. Inorganic, organic, and biological hazards are estimated for waste water sources. Sensitivities to these hazards for human uses are estimated. The water recycling processes considered are humidity condensation, carbon dioxide reduction, waste oxidation, distillation, reverse osmosis, pervaporation, electrodialysis, ion exchange, carbon sorption, and electrochemical oxidation. Limitations and applications of these processes are evaluated in terms of water quality objectives. Computerized simulation of some of these chemical processes is examined. Recommendations are made for development of new water recycling technology and improvement of existing technology for near term application to life support systems for humans in space. The technological developments are equally applicable to water needs on earth, in regions where extensive water ecycling is needed or where advanced water treatment is essential to meet EPA health standards.

Herrmann, Cal C.↗

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these "oxygenated" compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing

Mansell, J. Matthew↗

Influence of Oxygenated Compounds on Reaction Products in a Microwave Plasma Methane Pyrolysis Assembly for Post-Processing of Sabatier Methane

The state-of-the-art Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS) in April 2010. The system is designed to accept carbon dioxide from the Carbon Dioxide Removal Assembly and hydrogen from the Oxygen Generation Assembly. The two gases are reacted in the CRA in a Sabatier reactor to produce water and methane. Venting of methane results in an oxygen resupply requirement of about 378 lbs per crew member per year. If the oxygen is supplied as water, the total weight for resupply is about 476 lb per crew member per year. For long-term missions beyond low Earth orbit, during which resupply capabilities will be further limited, recovery of hydrogen from methane is highly desirable. For this purpose, NASA is pursuing development of a Plasma Pyrolysis Assembly (PPA) capable of recovering hydrogen from methane. Under certain conditions, water vapor and carbon dioxide (nominally intended to be separated from the CRA outlet stream) may be present in the PPA feed stream. Thus, testing was conducted in 2010 to determine the effect of these oxygenated compounds on PPA performance, particularly the effect of inlet carbon dioxide and water variations on the PPA product stream. This paper discusses the test set-up, analysis, and results of this testing.

Mansell, J. Matthew↗

Silica–Derived Nanostructured Electrode Materials for ORR, OER, HER, CO 2 RR Electrocatalysis, and Energy Storage Applications: A Review**

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords “silica”, “electrocatalysts”, “ORR”, “OER”, “HER”, “HOR”, “CO 2 RR”, “batteries”, and “supercapacitors”. The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO 2 RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.

25 ENERGY STORAGE↗

Developmental Efforts of an Electrochemical Oxygen Recovery System for Advanced Life Support

The current State of Art (SOA) Environmental Control and Life Support System (ECLSS) oxygen recovery system onboard the International Space Station (ISS) is complex, heavy, and power consuming system that recovers approximately 50% of the oxygen (O2) from metabolic carbon dioxide (CO2). For future long-duration missions, O2 recovery systems will need to be highly reliable, efficient, and recover maximum metabolic CO2. A minimum of 75% O2 recovery is required for future O2 recovery systems. Investigations into various technologies to help meet these requirements for exploration are ongoing; however, most of these proposed technologies ultimately result in a more complex system. A Macrofluidic Electrochemical Reactor (MFECR) is one proposed technology development effort currently underway at NASA Marshall Space Flight Center (MSFC) that has the potential to significantly reduce the complexity of ECLSS O2 recovery system. The MFECR operates at standard conditions, giving it an advantage over other technologies being investigated, which require high temperatures resulting in heavy reactors and high power consumption. The MFECR would replace three pieces of hardware for future ECLSS architectures: the current Carbon Dioxide Reduction Assembly (Sabatier reactor), the Plasma Pyrolysis Assembly (PPA), and the Oxygen Generation Assembly (OGA). It is designed to interface directly with the Carbon Dioxide Removal Assembly (CDRA) and the Water Processor Assembly (WPA). This allows for a less complex system and higher reliability than the current SOA as well as reduced power, weight and H2O consumption of ECLSS. Here, we will discuss the current technology development efforts of the MFECR and how this technology may aide in the advancement of future long-duration life support systems.

Brown, Brittany R.↗

Developmental Efforts of an Electrochemical Oxygen Recovery System for Advanced Life Support

The current State of Art (SOA) Environmental Control and Life Support System (ECLSS) oxygen recovery system onboard the International Space Station (ISS) is a complex, heavy, and power consuming system that recovers approximately 50% of the oxygen (O2) from metabolic carbon dioxide (CO2). For future long-duration missions, O2recovery systems will need to be highly reliable, efficient, and recover maximum metabolic CO2. Investigations into various technologies to help meet these requirements for exploration are ongoing; however, most of these proposed technologies ultimately result in a more complex system. A Macrofluidic Electrochemical Reactor (MFECR) is one proposed technology development effort currently underway at NASA Marshall Space Flight Center (MSFC) that has the potential to significantly reduce the complexity of ECLSSO2recovery system. The MFECR operates at standard conditions, giving it an advantage over other technologies being investigated, which require high temperatures resulting in heavy reactors and high power consumption. The MFECR would replace three pieces of hardware for future ECLSS architectures: the current Carbon Dioxide Reduction Assembly (Sabatier reactor), the Plasma Pyrolysis Assembly (PPA), and the Oxygen Generation Assembly(OGA). It is designed to interface directly with the Carbon Dioxide Removal Assembly (CDRA) and the Water Processor Assembly (WPA). This allows for a less complex system and higher reliability than the current SOA as well as reduced power, weight and H2Oconsumption of ECLSS. Here, we will discuss the current development efforts of the MFECR and how this technology may aide in the advancement of future long-duration life support systems.

Brittany R Brown↗

Multistep catalytic abiotic CO2 conversion to sugars through C1 intermediates

Carbon dioxide (CO2) to multicarbon (Cn) upgrading for commodity chemicals, fuel production, or artificial food synthesis using renewable energy input is a golden target for researchers in sustainable carbon emission reduction. Here, we explore and analyze a flexible modular roadmap for the task, utilizing sequential electro-, photo-, and organocatalysis to develop a strategy for CO2 conversion using the key and elusive formaldehyde precursor of interest for sugar generation. We study the electrochemical carbon dioxide reduction reaction to methanol in a flow cell and its discontinuous photooxidation to formaldehyde (PMOR) with excellent selectivity. Utilizing a highly active N-heterocyclic carbene catalyst enables tunable generation of C4-C6 aldoses without undesirable byproducts, with carbon conversion yield reaching 60 to 80% for desired pentose, tetrose, and triose product mixtures and over 20% for hexose. This approach presents a roadmap for CO2 valorization, aiming to bridge carbon waste streams with sustainable sugar synthesis and opening broad avenues for green chemical production.

CO2 valorization↗

How to Minimize Faradaic Efficiency Error in Electrochemical CO 2 Reduction for Gas Products

Faradaic efficiency (FE) is an important metric for evaluating electrochemical processes, such as carbon dioxide reduction, that is often used for performance comparisons. Although the equation to calculate FE is well-known, details needed to yield accurate values are often overlooked, potentially leading to errors exceeding 100%. Avoiding any errors is crucial for drawing correct conclusions, especially during a catalysis optimization process. Factors with high potential for FE errors include incorrect mass flow rates and temperature values, imprecise gas chromatography calibrations, and uncorrected gas viscosities, while factors with less potential are also identified. In conclusion, this manuscript presents FE calculation guidelines intended for both newcomers and experts in the field of electrochemical fuel production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploring the influence of interfacial solvation on electrochemical CO 2 reduction using plasmon‐enhanced vibrational sum frequency generation spectroscopy

Although interfacial solvation plays an important role in determining carbon dioxide reduction (CO 2 R) kinetics, present understanding of the potential dependent properties of the electrochemical double layer under conditions relevant for CO 2 R remains limited. This article summarizes the development and recent applications of plasmon-enhanced vibrational sum frequency generation (VSFG) spectroscopy to study the effects of cation hydration and interfacial solvation on CO 2 R using CO as a vibrational Stark reporter. Results show that electrolyte cations retain their entire solvation shell upon adsorption to inactive sites, while active sites retain only a single water layer between the gold surface and the cation. Measurements also show that the total interfacial electric field can be separated into two contributions: one from the electrochemical double layer (Stern field) and another from the polar solvation environment (Onsager field). Surprisingly, correlating VSFG spectra with reaction kinetics reveals that it is the solvation-mediated Onsager field that governs the chemical reactivity at the electrode/electrolyte interface. Measuring the interfacial water spectra during electrocatalysis also provides evidence for the proton source during H2 evolution, which competes with CO 2 R in aqueous electrolyte. These findings highlight the importance of directly probing cation hydration and interfacial solvation, which mediates reaction kinetics at electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct observation of the local microenvironment in inhomogeneous CO 2 reduction gas diffusion electrodes via versatile pOH imaging

In this study, we report how the micrometer-scale morphology of a carbon dioxide reduction (CO 2 R) gas diffusion electrode (GDE) affects the mass transport properties and with it, the local CO 2 R performance. We developed a technique to probe the microenvironment in a CO 2 R GDE via local pOH imaging with time- and three-dimensional spatial, micrometer-scale resolution. The local activity of hydroxide anions (OH - ), represented by the pOH value, around a GDE in contact with an aqueous electrolyte is a crucial parameter that governs the catalytic activity and CO 2 R selectivity. Here, we use fluorescence confocal laser scanning microscopy (CLSM) to create maps of the local pOH around a copper GDE by combining two ratiometric fluorescent dyes, one of which is demonstrated as a pOH sensor for the first time in this work. We observe that the local pOH decreases when current is applied due to the creation of OH - as a byproduct of CO 2 R. Interestingly, the pOH is lower inside microtrenches compared to the electrode surface and decreases further as trenches become more narrow due to enhanced trapping of OH - . We support our experimental results with multiphysics simulations that correlate exceptionally well with measurements. These simulations additionally suggest that the decreased pOH inside microcavities in the surface of a CO 2 R GDE leads to locally enhanced selectivity towards multicarbon (C 2+ ) products. This study suggests that narrow microstructures on the length scale of 5 μm in a GDE surface serve as local CO 2 R hotspots, and thus highlights the importance of a GDE's micromorphology on the CO 2 R performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomically Dispersed Ni‐N‐C Catalysts for Electrochemical CO 2 Reduction

Abstract The atomic dispersion of nickel in Ni‐N‐C catalysts is key for the selective generation of carbon monoxide through the electrochemical carbon dioxide reduction reaction (CO 2 RR). Herein, the study reports a highly selective, atomically dispersed Ni 1.0% ‐N‐C catalyst with reduced Ni loading compared to previous reports. Extensive materials characterization fails to detect Ni crystalline phases, reveals the highest concentration of atomically dispersed Ni metal, and confirms the presence of the proposed Ni‐N x active site at this reduced loading. The catalyst shows excellent activity and selectivity toward CO generation, with a faradaic efficiency for CO generation (FE CO ) of 97% and partial current density for CO (j co ) of ‐9.0 mA cm −2 at ‐0.9 V in an electrochemical H‐type cell. CO 2 RR activity and selectivity are also studied by rotating disk electrode (RDE) measurements where transport limitations can be suppressed. It is expected that the utility of these Ni‐N‐C catalysts will lie with tandem CO 2 RR reaction schemes to multi‐carbon (C 2+ ) products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of an Atmosphere Revitalization Subsystem for Deep Space Exploration Missions

An Atmosphere Revitalization Subsystem (ARS) suitable for deployment aboard deep space exploration mission vehicles has been developed and functionally demonstrated. This modified ARS process design architecture was derived from the International Space Station's (ISS) basic ARS. Primary functions considered in the architecture include trace contaminant control, carbon dioxide removal, carbon dioxide reduction, and oxygen generation. Candidate environmental monitoring instruments were also evaluated. The process architecture rearranges unit operations and employs equipment operational changes to reduce mass, simplify, and improve the functional performance for trace contaminant control, carbon dioxide removal, and oxygen generation. Results from integrated functional demonstration are summarized and compared to the performance observed during previous testing conducted on an ISS-like subsystem architecture and a similarly evolved process architecture. Considerations for further subsystem architecture and process technology development are discussed.

Perry, Jay L.↗

Filtration of Carbon Particulate Emissions from a Plasma Pyrolysis Assembly

NASA is investigating plasma pyrolysis as a candidate technology that will enable the recovery of hydrogen from the methane produced by the ISS Sabatier Reactor. The Plasma Pyrolysis Assembly (PPA) is the current prototype of this technology which converts the methane product from the Carbon Dioxide Reduction Assembly (CRA) to acetylene and hydrogen with 90% or greater conversion efficiency. A small amount of solid carbon particulates are generated as a side product and must be filtered before the acetylene is removed and the hydrogen-rich gas stream is recycled back to the CRA. We discuss developmental work on several options for filtering out the carbon particulate emissions from the PPA exit gas stream. The filtration technologies and concepts investigated range from fibrous media to monolithic ceramic and sintered metal media. This paper describes the different developed filter prototypes and characterizes their performance from integrated testing at the Environmental Chamber (E-Chamber) at MSFC. In addition, characterization data on the generated carbon particulates, that help to define filter requirements, are also presented.

methane↗

Sustainable Resource Recovery from Trash, Waste, and Overboard Venting

Space travel and planetary missions for long-endurance human presence require Environmental Control and Life Support (ECLS) loop-closure. The air and water resource loops are generally closed with their processes having been established through extensive development, testing, and long-term use on International Space Station. Closure of the air and water loops have enabled oxygen and hydrogen sustainability. Carbon sustainability has yet to be addressed. Waste and trash, which also contains hydrogen and oxygen and abundant carbon have not been developed to the extent air and water have. Waste and trash have generally been dealt with in terms of simple safening, storage, and disposal. In externally disposing of waste, which includes C1 and C2 hydrocarbon gases, lost resources not only increase mission cost they can result in space and planetary pollution that can lead to unfavorable public opinion. With all this in mind, we explore the idea of carbon sustainability within closed-cycle waste, trash, and C1/C2 reprocessing. Starting from the current ECLS System roadmap, we identify resources that are not yet captured in closed-cycle processes but are lost when crossing the thermodynamic boundaries of an open system. Such pseudo-resources are trash, waste, and the gaseous carbon products of carbon dioxide reduction. We then consider different means and processes for minimizing pseudo-resource loss so as to “close the carbon loop.” There are cases in which pseudo-resources need to be externally discarded, such as reducing spacecraft acceleration mass. In this case we examine various processes that can be beneficial to missions even when these pseudo-resources are lost. An example would be the conversion of waste into propellant, which can produce thrust while at the same time reducing mass for transit acceleration (and ultimately propellant mass at launch), in which case we propose a means for evaluating the value of converting waste into propellant for different propulsion systems.

waste↗

Kinetic Model Development of the Carbon Vapor Deposition Reactor to Predict Performance Versus Design

To enable complete closure of a Sabatier-based atmosphere revitalization system where oxygen recovery is predicated by carbon dioxide reduction to methane and water, there must be a means of recovering the hydrogen from the byproduct methane. Honeywell’s carbon vapor deposition (CVD) reactor is a potential technology that provides a thermochemical means by which methane decomposes at high temperatures (> 1,000 °C) into hydrogen, solid carbon, and a small percentage of hydrocarbons. This advanced methane pyrolysis reactor utilizes a carbon fiber substrate to capture and immobilize the solid pyrolytic carbon rather than allowing continuation toward undesirable soot. The CVD reactor is a highly dynamic system whose characteristic geometry changes while operating. The reactor model was developed to provide predictive performance assessment capabilities at different operating conditions, geometries, and configurations to aid in technology development. Modeling of the CVD reactor considered the multitude of simultaneous and interdependent physicochemical processes that are entailed, including: (1) the homogeneous gas-phase pyrolysis reactions, (2) the heterogeneous deposition reactions, and (3) the transport of gaseous species in the reactor domains. A 1-D CVD reactor model was developed based on a general packed-bed, axial-dispersion plug flow reactor model with a solid substrate balance to account for carbon deposition. The model includes 59 species and 243 reactions constituting the methane pyrolysis reaction network, carbon deposition, and interconversions of oxygenate species. The reactor model was compared to brassboard test data, where it was shown to be able to capture the pertinent physicochemical phenomena as evidenced by its agreement with short-duration run data (i.e., looking at different temperature and flow rate conditions), as well as trend agreement with the brassboard reactor’s long-duration test data. Recommendations are provided on further model development steps as well as its use cases.

Air Revitalization↗