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At least 145 records · Page 8

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon, is capable of recovering all the oxygen from carbon dioxide, and it is a promising alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon, and the resulting carbon buildup eventually fouls the catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

ECLSS↗

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50 because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Oxygen Recovery↗

Advanced air revitalization system testing

A previously developed experimental air revitalization system was tested cyclically and parametrically. One-button startup without manual interventions; extension by 1350 hours of tests with the system; capability for varying process air carbon dioxide partial pressure and humidity and coolant source for simulation of realistic space vehicle interfaces; dynamic system performance response on the interaction of the electrochemical depolarized carbon dioxide concentrator, the Sabatier carbon dioxide reduction subsystem, and the static feed water electrolysis oxygen generation subsystem, the carbon dioxide concentrator module with unitized core technology for the liquid cooled cell; and a preliminary design for a regenerative air revitalization system for the space station are discussed.

Heppner, D. B.↗

Characterization of Carbon Particulates in the Exit Flow of a Plasma Pyrolysis Assembly (PPA) Reactor

The ISS presently recovers oxygen from crew respiration via a Carbon Dioxide Reduction Assembly (CRA) that utilizes the Sabatier chemical process to reduce captured carbon dioxide to methane (CH4) and water. In order to recover more of the hydrogen from the methane and increase oxygen recovery, NASA Marshall Space Flight Center (MSFC) is investigating a technology, plasma pyrolysis, to convert the methane to acetylene. The Plasma Pyrolysis Assembly (or PPA), achieves 90% or greater conversion efficiency, but 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. In this work, we present the experimental results of an initial characterization of the carbon particulates in the PPA exit gas stream. We also present several potential options to remove these carbon particulates via carbon traps and filters to minimize resupply mass and required downtime for regeneration.

Methane pyrolysis↗

Chemical and Structural Evolution of AgCu Catalysts in Electrochemical CO 2 Reduction

Silver–copper (AgCu) bimetallic catalysts hold great potential for electrochemical carbon dioxide reduction reaction (CO 2 RR), which is a promising way to realize the goal of carbon neutrality. Although a wide variety of AgCu catalysts have been developed so far, it is relatively less explored how these AgCu catalysts evolve during CO 2 RR. The absence of insights into their stability makes the dynamic catalytic sites elusive and hampers the design of AgCu catalysts in a rational manner. Here, in this study, we synthesized intermixed and phase-separated AgCu nanoparticles on carbon paper electrodes and investigated their evolution behavior in CO 2 RR. Our time-sequential electron microscopy and elemental mapping studies show that Cu possesses high mobility in AgCu under CO 2 RR conditions, which can leach out from the catalysts by migrating to the bimetallic catalyst surface, detaching from the catalysts, and agglomerating as new particles. Besides, Ag and Cu manifest a trend to phase-separate into Cu-rich and Ag-rich grains, regardless of the starting catalyst structure. The composition of the Cu-rich and Ag-rich grains diverges during the reaction and eventually approaches thermodynamic values, i.e., Ag 0.88 Cu 0.12 and Ag 0.05 Cu 0.95 . The separation between Ag and Cu has been observed in the bulk and on the surface of the catalysts, highlighting the importance of AgCu phase boundaries for CO 2 RR. In addition, an operando high-energy-resolution X-ray absorption spectroscopy study confirms the metallic state of Cu in AgCu as the catalytically active sites during CO 2 RR. Taken together, this work provides a comprehensive understanding of the chemical and structural evolution behavior of AgCu catalysts in CO 2 RR.

Chen, Peng-Cheng↗

Metallene-related materials for electrocatalysis and energy conversion

As a member of graphene analogs, metallenes are a class of two-dimensional materials with atomic thickness and well-controlled surface atomic arrangement made of metals or alloys. When utilized as catalysts, metallenes exhibit distinctive physicochemical properties endowed from the under-coordinated metal atoms on the surface, making them highly competitive candidates for energy-related electrocatalysis and energy conversion systems. Significantly, their catalytic activity can be precisely tuned through the chemical modification of their surface and subsurface atoms for efficient catalyst engineering. Here, this minireview summarizes the recent progress in the synthesis and characterization of metallenes, together with their use as electrocatalysts toward reactions for energy conversion. In the Synthesis section, we pay particular attention to the strategies designed to tune their exposed facets, composition, and surface strain, as well as the porosity/cavity, defects, and crystallinity on the surface. We then discuss the electrocatalytic properties of metallenes in terms of oxygen reduction, hydrogen evolution, alcohol and acid oxidation, carbon dioxide reduction, and nitrogen reduction reaction, with a small extension regarding photocatalysis. At the end, we offer perspectives on the challenges and opportunities with respect to the synthesis, characterization, modeling, and application of metallenes.

36 MATERIALS SCIENCE↗

Phase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd Nanoparticles

Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Furthermore, we report the preparation of Pd nanoparticles with an unconventional hexagonal close-packed (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core–shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core–shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepared. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochemical carbon dioxide reduction reaction (CO 2 RR) for production of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from –0.9 to –0.4 V (versus the reversible hydrogen electrode), which is among the best reported CO 2 RR catalysts in H-type electrochemical cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prototype Bosch CO2 reduction subsystem for the RLSE experiment

Requirements for the Bosch carbon dioxide reduction subsystem were established in a study of regenerative life support evaluation experiments. A detailed design is presented including a schematic, components list and characteristics, requirements summaries, and complete definition of life systems' advanced control/monitor instrumentation applied to the Bosch subsystem. Design information needed to proceed with the final design and fabrication of a preprototype system is presented.

Heppner, D. B.↗

Integrated testing of an electrochemical depolarized CO2 concentrator /EDC/ and a Bosch CO2 reduction subsystem /BRS/

An oxygen reclamation system (ORS) in a spacecraft has the task to revitalize the spacecraft atmosphere by recovering the elementary oxygen from metabolically produced carbon dioxide and water vapor. Life support subsystems which can form such an ORS are an electrochemical depolarized carbon dioxide concentrator (EDC), a Bosch carbon dioxide reduction subsystem (BRS), and an oxygen generation subsystem (OGS). A total recovery of the oxygen from metabolically generated carbon dioxide can be obtained with the aid of system composed of the considered three subsystems. Attention is given to the control concept which assures an integrated operation of the EDC, BRS, and OGS. A description is presented of the test results obtained during 86 days of testing.

Schubert, F. H.↗

Carbon dioxide and nitrogen reduction reactions using 2D transition metal dichalcogenide (TMDC) and carbide/nitride (MXene) catalysts

Improving the carbon dioxide and nitrogen reduction reactions (CO 2 RR and NRR) can reduce anthropogenic greenhouse gas emissions while selectively producing chemicals needed for the fuel, plastic, and chemical industries. Efficient CO 2 RR can be used to replace fossil fuels as well as repurpose captured CO 2 , while new NRR pathways can be used to supplement or replace the energy intensive Haber–Bosch process for NH 3 generation with no CO 2 emissions. Therefore, this review article focuses on (photo)electrocatalytic and photocatalytic conversion of CO 2 and N 2 molecules into useful products, such as carbon monoxide, methanol, formic acid, and ammonia, using 2D transition metal dichalcogenides (TMDCs) and metal carbides/nitrides (MXenes). Additionally, these highly tunable 2D catalysts will be evaluated for their ability to selectively and efficiently undergo CO 2 RR and NRR by controlling defects, phases, edge sites, interfaces, and functional groups. We first address the CO 2 RR and NRR challenges, with a particular focus on theoretical mechanisms and minimum energy pathways. We follow this discussion with a detailed review of state-of-the-art 2D TMDC and MXene experimental catalysts for CO 2 RR and NRR (photo)electrocatalytic and photocatalytic reactions, and then address areas of opportunity for these catalytic reactions.

14 SOLAR ENERGY↗

Monitoring and control of atmosphere in a closed environment

Applications requiring new technologies for atmosphere monitoring and control in the closed environment and their principal functions aboard the Space Station Freedom are described. Oxygen loop closure, involving the conversion of carbon dioxide to oxygen; carbon dioxide reduction and removal; and monitoring of atmospheric contamination are discussed. The Trace Contaminant Monitor, the Major Constituent Analyzer, the Carbon Dioxide Monitor, and the Particulate Counter Monitor are discussed.

Humphries, R.↗

Plasma Pyrolysis Assembly Regeneration Evaluation

In April 2010 the Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS). This technology requires hydrogen to recover oxygen from carbon dioxide. This results in the production of water and methane. Water is electrolyzed to provide oxygen to the crew. Methane is vented to space resulting in a loss of valuable hydrogen and unreduced carbon dioxide. This is not critical for ISS because of the water resupply from Earth. However, in order to have enough oxygen for long-term missions, it will be necessary to recover the hydrogen to maximize oxygen recovery. Thus, the Plasma Pyrolysis Assembly (PPA) was designed to recover hydrogen from methane. During operation, the PPA produces small amounts of carbon that can ultimately reduce performance by forming on the walls and windows of the reactor chamber. The carbon must be removed, although mechanical methods are highly inefficient, thus chemical methods are of greater interest. The purpose of this effort was to determine the feasibility of chemically removing the carbon from the walls and windows of a PPA reactor using a pure carbon dioxide stream.

Medlen, Amber↗

Theoretical Investigation of the Adsorbate and Potential–Induced Stability of Cu Facets During Electrochemical CO 2 and CO Reduction

The activity and product selectivity of electrocatalysts for reactions like the carbon dioxide reduction reaction (CO 2 RR) are intimately dependent on the catalyst's structure and composition. While engineering catalytic surfaces can improve performance, discovering the key sets of rational design principles remains challenging due to limitations in modeling catalyst stability under operating conditions. Herein, we perform first-principles density functional calculations adopting implicit solvation methods with potential control to study the influence of adsorbates and applied potential on the stability of different facets of model Cu electrocatalysts. Using coverage dependencies extracted from microkinetic models, we describe an approach for calculating potential and adsorbate-dependent contributions to surface energies under reaction conditions, where Wulff constructions are used to understand the morphological evolution of Cu electrocatalysts under CO 2 RR conditions. Here we identify that CO*, a key reaction intermediate, exhibits higher kinetically and thermodynamically accessible coverages on (100) relative to (111) facets, which can translate into an increased relative stabilization of the (100) facet during CO 2 RR. Our results support the known tendency for increased (111) faceting of Cu nanoparticles under more reducing conditions and that the relative increase in (100) faceting observed under CO 2 RR conditions is likely attributed to differences in CO* coverage between these facets.

30 DIRECT ENERGY CONVERSION↗

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↗