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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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NASA NTRS2014

James Webb Space Telescope: The First Light Machine

NASA James Webb Space Telescope (JWST) will search for the first luminous objects of the Universe to help answer fundamental questions about how the Universe came to look like it does today. At 6.5 meters in diameter, JWST will be the world's largest space telescope. Its architecture, e.g. aperture, wavelength range and operating temperature, is driven by JWST's science objectives. Introduction: Scheduled to start its 5 year mission after 2018, JWST will study the origin and evolution of galaxies, stars and planetary systems. Its science mission is to: Identify the first bright objects that formed in the early Universe, and follow the ionization history. Determine how galaxies form. Determine how galaxies and dark matter, including gas, stars, metals, overall morphology and active nuclei evolved to the present day. Observe the birth and early development of stars and the formation of planets. And, study the physical and chemical properties of solar systems for the building blocks of Life. Principle: To accomplish the JWST science objectives requires a larger aperture infrared cryogenic space telescope. A large aperture is required because the objects are very faint. The infrared spectral range is required because the objects are so far away that their ultraviolet and visible wavelength spectral lines are red-shifted into the infrared. Because the telescope is infrared, it needs to be cryogenic. And, because of the telescope is infrared, it must operate above the Earth's atmosphere, i.e. in space. JWST is probably the single most complicated mission that humanity has attempted. It is certainly the most difficult optical fabrication and testing challenge of our generation. The JWST 6.5 m diameter primary mirror is nearly a parabola with a conic constant of -0.9967 and radius of curvature at 30K of 15.880 m. The primary mirror is divided into 18 segments with 3 different prescriptions; each with its own off-axis distance and aspheric departure. The radius of curvature for all 18 segments must match to +/- 0.150 mm at 30K. JWST is diffraction limited at 2 micrometers which translates into a transmitted wavefront specification of 156 nm rms. Of that amount, 50 nm rms is allocated to the primary mirror. Each segment is allocated 22 nm rms surface error. At the start of the JWST program, the capability to make such a mirror did not exist. In 1996, NASA began a systematic and comprehensive mirror technology development effort which resulted in JWST. This program resulted in a qualified mirror fabrication process being approved in 2006. Today, all JWST primary mirror segments meet their requirements and are on schedule for a 2018 launch. The next step is system level assembly, integration and test. Ambient tests will be conducted at Goddard Space Flight Center and cryogenic system level testing will be performed in Chamber A at the Johnson Space Center.

Stahl, H. Philip↗
NASA NTRS1993

Low-energy ion implantation: Large mass fractionation of argon

The isotropic signatures of noble gases in the atmospheres of the Earth and other planets are considerably evolved when compared to signatures observed in the solar wind. The mechanisms driving the evolution of planetary volatiles from original compositions in the solar accretion disk are currently poorly understood. Modeling of noble-gas compositional histories requires knowledge of fractionating processes that may have operated through the evolutionary stages. Since these gases are chemically inert, information on noble-gas fractionation processes can be used as probes. The importance of understanding these processes extends well beyond 'noble-gas planetology.' Trapped argon acquired by low-energy implantation (approximately less than 100 eV) into solids is strongly mass fractionated (approximately greater than or equal to 3 percent/amu). This has potential implications for the origin and evolution of terrestrial planet atmospheres.

Ponganis, K. V.↗
NASA NTRS1995

Earth observations from space: History, promise, and reality. Executive summary

In this report the Committee on Earth Studies (CES), a standing committee of the Space Studies Board (SSB) within the National Research Council (NRC), reviews the recent history (nominally from 1981 to 1995) of the U.S. earth observations programs that serve civilian needs. The principal observations programs examined are those of NASA and the National Oceanic and Atmospheric Administration (NOAA). The Air Force' s Defense Meteorological Satellite Program (DMSP) is discussed, but only from the perspective of its relationship to civil needs and the planned merger with the NOAA polar-orbiting system. The report also reviews the interfaces between the earth observations satellite programs and the major national and international environmental monitoring and research programs. The monitoring and research programs discussed are the U.S. Global Change Research Program (USGCRP), the International Geosphere-Biosphere Program (IGBP), the World Climate Research Program (WCRP), related international scientific campaigns, and operational programs for the sharing and application of environmental data. The purpose of this report is to provide a broad historical review and commentary based on the views of the CES members, with particular emphasis on tracing the lengthy record of advisory committee recommendations. Any individual topic could be the subject of an extended report in its own right. Indeed, extensive further reviews are already under way to that end. If the CES has succeeded in the task it has undertaken. This report will serve as a useful starting point for any such more intensive study. The report is divided into eight chapters: ( I ) an introduction, (2) the evolution of the MTPE, (3) its relationship to the USGCRP, (4) applications of earth observations data, (5) the role that smaller satellites can play in research and operational remote sensing, (6) earth system modeling and information systems, (7) a number of associated activities that contribute to the MTPE and the USGCRP, and (8) organizational issues in the conduct of civil earth observations programs. Following the body of the report is a series of appendixes: after a list of acronyms and abbreviations and collected short biographies of CES members, six brief tutorials discuss several scientific topics important to the science and applications of earth observations. Highlights from the eight chapters follow.

Source record↗
NASA NTRS2008

A Multi-Season Study of the Effects of MODIS Sea-Surface Temperatures on Operational WRF Forecasts at NWS Miami, FL

Studies at the Short-term Prediction Research and Transition (SPORT) Center have suggested that the use of Moderate Resolution Imaging Spectroradiometer (MODIS) sea-surface temperature (SST) composites in regional weather forecast models can have a significant positive impact on short-term numerical weather prediction in coastal regions. Recent work by LaCasse et al (2007, Monthly Weather Review) highlights lower atmospheric differences in regional numerical simulations over the Florida offshore waters using 2-km SST composites derived from the MODIS instrument aboard the polar-orbiting Aqua and Terra Earth Observing System satellites. To help quantify the value of this impact on NWS Weather Forecast Offices (WFOs), the SPORT Center and the NWS WFO at Miami, FL (MIA) are collaborating on a project to investigate the impact of using the high-resolution MODIS SST fields within the Weather Research and Forecasting (WRF) prediction system. The project's goal is to determine whether more accurate specification of the lower-boundary forcing within WRF will result in improved land/sea fluxes and hence, more accurate evolution of coastal mesoscale circulations and the associated sensible weather elements. The NWS MIA is currently running WRF in real-time to support daily forecast operations, using the National Centers for Environmental Prediction Nonhydrostatic Mesoscale Model dynamical core within the NWS Science and Training Resource Center's Environmental Modeling System (EMS) software. Twenty-seven hour forecasts are run dally initialized at 0300, 0900, 1500, and 2100 UTC on a domain with 4-km grid spacing covering the southern half of Florida and adjacent waters of the Gulf of Mexico and Atlantic Ocean. Each model run is initialized using the Local Analysis and Prediction System (LAPS) analyses available in AWIPS. The SSTs are initialized with the NCEP Real-Time Global (RTG) analyses at 1/12deg resolution (approx.9 km); however, the RTG product does not exhibit fine-scale details consistent with its grid resolution. SPORT is conducting parallel WRF EMS runs identical to the operational runs at NWS MIA except for the use of MODIS SST composites in place of the RTG product as the initial and boundary conditions over water, The MODIS SST composites for initializing the SPORT WRF runs are generated on a 2-km grid four times daily at 0400, 0700, 1600, and 1900 UTC, based on the times of the overhead passes of the Aqua and Terra satellites. The incorporation of the MODIS SST data into the SPORT WRF runs is staggered such that SSTs are updated with a new composite every six hours in each of the WRF runs. From mid-February to July 2007, over 500 parallel WRF simulations have been collected for analysis and verification. This paper will present verification results comparing the NWS MIA operational WRF runs to the SPORT experimental runs, and highlight any substantial differences noted in the predicted mesoscale phenomena for specific cases.

Case, Jonathan L.↗
DOE OSTI2018

Nanoalloy catalysts inside fuel cells: An atomic-level perspective on the functionality by combined in operando x-ray spectroscopy and total scattering

We introduce an experimental approach for structural characterization of catalysts for fuel cells combining synchrotron x-ray spectroscopy and total scattering. The approach allows probing catalysts inside operating fuel cells with atomic-level precision (~ 0.02 Å) and element specificity (~ 2–3 at%) in both time (~ 1 min) and space (~ μm) resolved manner. The approach is demonstrated on exemplary Pd-Sn and Pt-Ni-Cu nanoalloy catalysts for the oxygen reduction reaction (ORR) deposited on the cathode of an operating proton exchange membrane fuel cell. In operando x-ray data show that under operating conditions, the catalyst particles can undergo specific structural changes, ranging from sub-Å atomic fluctuations and sharp nanophase transitions to a gradual strain relaxation and growth, which inflict significant losses in their ORR activity. Though triggered electrochemically, the changes are not driven solely by differences in the reduction potential and surface energy of the metallic species constituting the nanoalloys but also by the formation energy of competing nanophases, mismatch between the size of individual atomic species and their ability to interdiffuse fast in search of energetically favorable configurations. Given their complexity, the changes are difficult to predict and so the resulting ORR losses remain difficult to limit. We show that in operando knowledge of the structural evolution of nanoalloy catalysts helps create strategies for improving their activity and stability. In particular, we show that shaping Pd-Sn nanoalloys rich in Pd as cubes reduces the interdiffusion of atoms at their surface and so makes them better catalysts for ORR in fuel cells in comparison to other Pd-Sn nanoalloys. In addition, we demonstrate that the approach introduced here can provide knowledge of other major factors affecting the performance of fuel cells such as operating temperature and the overall catalyst utilization, in particular the evolution of elemental and mass distribution of catalyst particles over the cells’ cathode. Last but not least, we discuss how in operando x-ray spectroscopy and total x-ray scattering can bridge the knowledge gap between the widely used in situ SAXS, EXAFS and monocrystal surface XRD techniques for structural characterization of nanoalloy catalysts explored for energy related applications.

25 ENERGY STORAGE↗
DOE OSTI2024

The hierarchical structure of organic mixed ionic–electronic conductors and its evolution in water

Polymeric organic mixed ionic–electronic conductors underpin several technologies in which their electrochemical properties are desirable. These properties, however, depend on the microstructure that develops in their aqueous operational environment. We investigated the structure of a model organic mixed ionic–electronic conductor across multiple length scales using cryogenic four-dimensional scanning transmission electron microscopy in both its dry and hydrated states. Four-dimensional scanning transmission electron microscopy allows us to identify the prevalent defects in the polymer crystalline regions and to analyse the liquid crystalline nature of the polymer. The orientation maps of the dry and hydrated polymers show that swelling-induced disorder is mostly localized in discrete regions, thereby largely preserving the liquid crystalline order. Therefore, the liquid crystalline mesostructure makes electronic transport robust to electrolyte ingress. Furthermore, this study demonstrates that cryogenic four-dimensional scanning transmission electron microscopy provides multiscale structural insights into complex, hierarchical structures such as polymeric organic mixed ionic–electronic conductors, even in their hydrated operating state.

36 MATERIALS SCIENCE↗
NASA NTRS1975

The evolution of the SEASAT imaging radar

The paper describes the design parameters and development of a synthetic aperture radar for use on the SEASAT spacecraft. This imaging radar is designed to operate at altitudes of 800 km with an orbital inclination of 108 deg, a nominal resolution of 25 m, and a swath width of 100 km. The design evolved from planetary imaging radar studies conducted over many years where an L-band imaging radar was developed and tested on aircraft flights as a prototype system to map the surface of Venus. A solid-state transmitter is used where the pulse repetition frequency is a function of altitude and will be about 2kHz for a 12-m long antenna. The receiver consists of the receiver protector, input filters, the gain control, and the RF amplifier. The ground station uses the standard NASA receiver with a 10-m antenna. The correlator, either optical or digital, must be able to compensate for the pitch and yaw variations of the spacecraft as well as the inherent effective yaw caused by the rotation of the earth, and extract the range curvature and range walk effects.

Brown, W. E., Jr.↗
NASA NTRS1985

Evolution of area access safety training required for gaining access to Space Shuttle launch and landing facilities

Assuring personnel and equipment are fully protected during the Space Shuttle launch and landing operations has been a primary concern of NASA and its associated contractors since the inception of the program. A key factor in support of this policy has been the area access safety training requirements for badging of employees assigned to work on Space Shuttle Launch and Facilities. This requirement was targeted for possible cost savings and the transition of physical on-site walkdowns to the use of television tapes has realized program cost savings while continuing to fully satisfy the area access safety training requirements.

Willams, M. C.↗
NASA NTRS2013

Evolution of International Space Station Program Safety Review Processes and Tools

The International Space Station Program at NASA is constantly seeking to improve the processes and systems that support safe space operations. To that end, the ISS Program decided to upgrade their Safety and Hazard data systems with 3 goals: make safety and hazard data more accessible; better support the interconnection of different types of safety data; and increase the efficiency (and compliance) of safety-related processes. These goals are accomplished by moving data into a web-based structured data system that includes strong process support and supports integration with other information systems. Along with the data systems, ISS is evolving its submission requirements and safety process requirements to support the improved model. In contrast to existing operations (where paper processes and electronic file repositories are used for safety data management) the web-based solution provides the program with dramatically faster access to records, the ability to search for and reference specific data within records, reduced workload for hazard updates and approval, and process support including digital signatures and controlled record workflow. In addition, integration with other key data systems provides assistance with assessments of flight readiness, more efficient review and approval of operational controls and better tracking of international safety certifications. This approach will also provide new opportunities to streamline the sharing of data with ISS international partners while maintaining compliance with applicable laws and respecting restrictions on proprietary data. One goal of this paper is to outline the approach taken by the ISS Progrm to determine requirements for the new system and to devise a practical and efficient implementation strategy. From conception through implementation, ISS and NASA partners utilized a user-centered software development approach focused on user research and iterative design methods. The user-centered approach used on the new ISS hazard system utilized focused user research and iterative design methods employed by the Human Computer Interaction Group at NASA Ames Research Center. Particularly, the approach emphasized the reduction of workload associated with document and data management activities so more resources can be allocated to the operational use of data in problem solving, safety analysis, and recurrence control. The methods and techniques used to understand existing processes and systems, to recognize opportunities for improvement, and to design and review improvements are described with the intent that similar techniques can be employed elsewhere in safety operations. A second goal of this paper is to provide and overview of the web-based data system implemented by ISS. The software selected for the ISS hazard systemMission Assurance System (MAS)is a NASA-customized vairant of the open source software project Bugzilla. The origin and history of MAS as a NASA software project and the rationale for (and advantages of) using open-source software are documented elsewhere (Green, et al., 2009).

Ratterman, Christian D.↗
NASA NTRS1993

Manned Space-laboratories Control Center (MSCC) operations concept

The initiation of the (German-) nationally funded control center for manned spaceflight operations triggered by the invitation of President Reagan to ESA, Japan, and Canada in 1984 to join the International Space Station Freedom Program is recalled. The requirements for a Manned Space-Laboratories Control Center (MSCC) as defined at the beginning of the planning and construction process in 1987 and the resulting modifications during the various programmatic scenario changes on NASA and ESA side between 1987 and now are presented. The validity of the original requirements with respect to the current scenario, which asks for a logical evolution from the execution of the D-2 mission in January 1993 via the European Columbus Precursor flights (in particular the E-1 mission) towards Columbus Attached Laboratory (APM)-operations by the end of this century are discussed. The resulting tasks of the MSCC for the various missions, the current configuration, and the ensuing operations concept leading from a more centralized concept for D-2 towards a decentralized payload operations concept for the APM and the implications with respect to European and International interfaces are presented. The planned Columbus MSCC facility architecture and its expected modifications introduced by the ESA Ministerial Conference in Munich (Nov. 1991) and follow-on discussions are briefly addressed. The last chapter outlines the planned services to be provided by the MSCC to the decentralized User (experimenter) community. Issues like decentralized mission planning on executional level, command validation, data flow coordination, archiving services, and telescience capabilities are highlighted from a MSCC point of view.

Kehr, Joachim↗
NASA NTRS2012

Orbit Transfers for Dawn's Vesta Operations : Navigation and Mission Design Experience

Dawn, a mission belonging to NASA's Discovery Program, was launched on September 27, 2007 to explore main belt asteroids in order to yield insights into important questions about the formation and evolution of the solar system. From July of 2011 to August of 2012, the Dawn spacecraft successfully returned valuable science data, collected during the four planned mapping orbits at its first target asteroid, Vesta. Each mapping orbit was designed to enable a different set of scientific observations. Such a mission would have been impossible without the low thrust ion propulsion system (IPS). Maneuvering a spacecraft using only the IPS for the transfers between the mapping orbits posed many technical challenges to Dawn's flight team at NASA's Jet Propulsion Laboratory. Each transfer needs a robust plan that accounts for uncertainties in maneuver execution, orbit determination, and physical characteristics of Vesta. This paper discusses the mission design and navigational experience during Dawn's Vesta operations. Topics include requirements and constraints from Dawn's science and spacecraft teams, orbit determination and maneuver design and building process for transfers, developing timelines for thrust sequence build cycles, and the process of scheduling very demanding coverage with ground antennae at NASA's Deep Space Network.

low thrust↗
DOE OSTI2017

Multiferroic and Related Hysteretic Behavior in Ferromagnetic Shape Memory Alloys

In this work, we combine a Ginzburg–Landau model for a ferroelastic transition with the theory of micromagnetism to study the magnetostructural behavior leading to multicaloric effects in ferromagnetic shape memory alloys. We analyze the ferroelastic transition under different conditions of temperature, stress and magnetic field and establish the corresponding phase diagram. On the one hand, our results show that the proper combination of both fields may be used to reduce the transition hysteresis and thus improve the reversibility of the related elastocaloric effects, superelasticity and stress-mediated magnetocaloric effects. On the other hand, the stress-free magnetic field-driven and thermally driven magnetostructural evolution provides physical insight into the low-temperature field-induced domain reorientation, from which we derive strategies to modify the operational temperature ranges and thus the corresponding (magnetic) shape-memory effect.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Quantum Fokker-Planck modeling of degenerate electrons

In this work, an implicit and conservative numerical scheme is proposed for the isotropic quantum Fokker-Planck equation describing the evolution of degenerate electrons subject to elastic collisions with other electrons and ions. The electron-ion and electron-electron collision operators are discretized using a discontinuous Galerkin method, and the electron energy distribution is updated by an implicit time integration method. The numerical scheme is designed to satisfy all conservation laws exactly. Numerical tests and comparisons with other modeling approaches are shown to demonstrate the accuracy and conservation properties of the proposed method.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Determining the effects of U/Pu ratio on subsolidus phase transitions in U-Pu-Zr metallic fuel alloys

Here, ternary alloys consisting primarily of uranium, plutonium, and zirconium (U-Pu-Zr) are among the leading candidate fuel systems considered for fast spectrum nuclear reactors. Despite historical operation data from the testing of U-Pu-Zr rods in the Experimental Breeder Reactor-II, considerable uncertainty about the evolution of phases and microstructure across the ternary composition space exists. Due to sluggish kinetics and other difficulties in handling metal actinide specimens, quantitative measurements of phase-transitions in U-Pu-Zr alloys remain sparse in scientific literature, with most investigators reporting either phase-transition temperatures or phase identification data, but not both from the same specimens. The purpose of this paper is to critically compare experimental and calculated phase transition data and correlate with the microstructure and phase characterization data of as-cast and annealed U-Pu-Zr alloys. Phase transition peaks were measured using differential scanning calorimetry in the subsolidus regions (723-948 K) of three ternary U-Pu-Zr alloys with the same zirconium concentration but various U/Pu ratios. Overlapping peaks were deconvoluted using a Frazier-Suzuki peak fitting algorithm, and the critical peak temperatures and enthalpies were calculated. In general, increasing concentrations of Pu were associated with enhanced thermal stability of the body-centered cubic γ phase upon both heating and cooling. Experimental phase transition temperatures in this study tended to agree well with the predictions of the established ternary phase diagrams and other reported phase transition temperatures in literature. Additionally, the TAF-ID thermodynamic database was used to calculate a U-Pu-40 at.% Zr pseudobinary diagram as well as ternary diagrams from 773 to 973 K. The equilibrium phase transition temperatures tended to be considerably lower than measured peak temperatures upon both heating and cooling. Recommendations for improving the quality of data in future U-Pu-Zr characterization studies are also discussed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Kinetically versus thermodynamically controlled factors governing elementary pathways of GaP(111) surface oxidation

GaP and related III-V semiconductors have attracted interest as high-efficiency photoelectrochemical electrodes for solar water splitting. However, their efficacy is linked to the presence, identity, and integrity of native surface oxides, which are structurally and chemically complex and evolve during operation. Using ambient pressure X-ray photoelectron spectroscopy (APXPS) coupled with ab initio simulations, we track key chemical motifs expressed during evolution of GaP(111) surface oxides, their associated reaction kinetics, and their correlations with electronic properties. We identify two distinct thermal regimes corresponding to kinetically and thermodynamically controlled oxidation. Below 600 K, exposure to O2 generates kinetically facile Ga-O-Ga configurations, whereas higher temperatures cause activated oxygen to insert into Ga–P bonds as part of a thermodynamically driven transformation into a complex, heterogeneous 3D network of surface POx (1≤x ≤ 4) groups and Ga2O3 species, the latter of which eventually dominates upon depletion of surface phosphorus. Here our study highlights the critical competition between kinetic and thermodynamic factors during GaP oxidation, yielding insights for fabricating stable III-P-based photoelectrodes with precisely engineered surface properties.

08 HYDROGEN↗
DOE OSTI2025

Thermodynamics, local structure, and transport of protons in triple-conducing oxide, BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ (BCFZY4411)

Triple-conducting oxides (TCOs) are an emerging class of mixed ionic and electronically conducting materials that show great promise for oxygen reduction/oxygen evolution (ORR/OER) electrocatalysis—primarily in high-temperature ceramic electrochemical cells— but also in aqueous alkaline environments. Their high activity is attributed, at least in part, to their ability to incorporate and transport three mobile charge carriers: protons, oxygen vacancies, and electron-holes Despite their promise, fundamental studies of TCOs are challenging, as transport dynamics from three charge carriers cannot be fully disentangled via traditional electrical measurement techniques. Characterizing proton dynamics in TCOs is particularly difficult as protons are generally the minority carrier, and their conduction response is typically obscured by the oxygen vacancies and electron holes. Here, we demonstrate successful isolation of the proton behavior in an archetypal TCO, BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ (BCFZY4411), using a combination of non-electrical techniques. We determine proton uptake and oxygen non-stoichiometry (δ) using thermogravimetric analysis (TGA). X-ray absorption near edge structure (XANES) and neutron diffraction (ND) are used to validate the oxidation state of Co and the δ values obtained through TGA. We apply 1H solid-state magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) to provide insights into local structure, dynamics, and proton kinetics. Finally, the proton transport properties are further quantified using tracer isotope exchange with time-of-flight secondary ion mass spectrometry (ToF-SIMS). Despite the very low proton concentrations in BCFZY4411 (<0.2% under most conditions), our analysis suggests that the oxygen Manuscript File Click here to view linked References 2 reduction and evolution reactions are nevertheless limited by the oxygen ion kinetics (e.g., oxygen surface exchange) rather than the proton kinetics at the reduced operating temperatures (<500 °C) that are targeted for electrochemical cell applications. These findings provide a comprehensive understanding of proton behavior in BCFZY4411 and pave the way for advancing the fundamental study of TCOs.

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

Potential Control of Oxygen Non-Stoichiometry in Cerium Oxide and Phase Transition Away from Equilibrium

Cerium oxide (ceria, CeO 2 ) is a technologically important material for energy conversion applications. Its activities strongly depend on redox states and oxygen vacancy concentration. Understanding the functionality of chemical active species and behavior of oxygen vacancy during operation, especially in high-temperature solid-state electrochemical cells, is the key to advance future material design. Herein, the structure evolution of ceria is spatially resolved using bulk-sensitive operando X-ray diffraction and spectroscopy techniques. During water electrolysis, ceria undergoes reduction, and its oxygen non-stoichiometry shows a dependence on the electrochemical current. Cerium local bonding environments vary concurrently to accommodate oxygen vacancy formation, resulting in changes in Ce-O coordination number and Ce 3+ /Ce 4+ redox couple. When reduced enough, a crystallographic phase transition occurs from α to an α' phase with more oxygen vacancies. Nevertheless, the transition behavior is intriguingly different from the one predicted in the standard phase diagram of ceria. This work demonstrates a feasible means to control oxygen non-stoichiometry in ceria via electrochemical potential. It also sheds light on the mechanism of phase transitions induced by electrochemical potential. For electrochemical systems, effects from a large-scale electrical environment should be taken into consideration, besides effective oxygen partial pressure and temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Cation Crossover Limits Accessible Current Densities for Zero-Gap Alkaline CO2 Reduction to Ethylene

Traditional CO2 reduction systems often fail in an alkaline environment due to the interaction of CO2 with a high-pH electrolyte, where carbonate and bicarbonate ion formation results in potassium-containing salt precipitation. The presence of the salt crystals causes a reduction in the selectivity of the electrolyzer toward CO2 conversion. Here, the critical operational variables, which elicit the salting out process, are investigated (i.e., ion transport). When the electrolyzer exceeds a critical current density, H2 evolution dominates CO2 reduction due to salt formation, which is confirmed by postmortem cross-sectional SEM-EDS of the electrode. The critical current density decreases with an increasing membrane thickness or anolyte ionic strength. Cathode salt formation is mediated by the unmitigated crossover of cations from the anolyte to the cathode across an anion exchange membrane, through which cations are imperfectly excluded. It is likely that electric field-driven migration promotes an increase in concentration of potassium across the membrane, until, at the critical current density for that electrolyzer arrangement, the concentration of potassium and bicarbonate ions exceeds the solubility limit of KHCO3, leading to salt precipitation.

CO2 reduction↗