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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Combined Rotating Disk Slurry Electrodeposition–Spontaneous Galvanic Displacement for Pt-M (M = Co, Ni, and Cu) Catalyst Synthesis for the Oxygen Reduction Reaction in Alkaline Media

Here, platinum-modified first-row transition-metal catalyst (M = Ni, Co, and Cu) nanoparticles on a carbon black Vulcan XC-72R (CBV) support were synthesized using rotating disk slurry electrodeposition (RoDSE) followed by spontaneous galvanic displacement (SGD) reactions. These RoDSE–SGD catalysts were evaluated for the oxygen reduction reaction (ORR) in 0.1 M KOH using rotating disk electrode techniques. The Ni and Co RoDSEs were done by using an electrochemical applied potential of -0.75 V versus the RHE and for Cu, -0.80 V versus the RHE using a CBV slurry solution containing 0.1 M KClO 4 . These metal nanoparticles on CBV (M/CBV) catalysts were modified with a Pt precursor via a spontaneous galvanic displacement (SGD) reaction, producing a Pt-M/CBV material to catalyze the ORR in an alkaline medium. High-resolution scanning transmission electron microscopy (HR-STEM) analysis indicates that the PtM/CBV samples include M clusters and Pt single atoms. The ORR characterization measurements were done under a controlled temperature (25.0 °C) and with a mass loading of 100 μg/cm 2 on a glassy carbon (GC) rotating disk electrode at 1600 rpm. The PtCo/CBV showed the highest ORR mass activity of 0.741 A/mgPt at 0.90 V versus the reversible hydrogen electrode (RHE) compared with commercial Pt/CBV. The M/CBV RoDSE catalysts were also tested for the oxygen evolution reaction (OER), and Ni/CBV provided the lowest overpotential of 450 mV at 10 mA/cm 2 disk in 0.1 M KOH.

30 DIRECT ENERGY CONVERSION↗

Electrolyzers in focus: advances in CO 2 electrolyzer designs

Electrochemical CO 2 reduction (ECR) remains a viable method to reintegrate anthropogenic CO 2 into current energy infrastructures through its conversion into commodity chemicals. To facilitate the integration of ECR, electrochemical devices called electrolyzers must be implemented to overcome the inherent limitations that exist in current ECR experiments, namely kinetics and mass transport. In this review, we outline the current and advancing designs in ECR electrolyzers, with a focus on the following five electrochemical devices: membrane electrode assemblies (MEA), flow cell (FC), rotating disk electrode (RDE), rotating ring-disk electrode (RRDE), and rotating cylinder electrode (RCE). We highlight the tunable components of each electrolyzer with a forward outlook on the optimization and relevance of electrolyzer designs in upcoming ECR applications.

CO2 reduction↗

Advanced Electrochemical Separations of Actinide/Fission Products via the Control of Nucleation and Growth of Electrodeposits. Final Report

This is the final report to the NEUP regarding the “Advanced Electrochemical Separations of Actinide/Fission products via the Control of Nucleation and Growth of Electrodeposits” project. This report describes the project activities conducted during the period October 01, 2016 through September 30, 2019. The report includes a brief statement of the project objectives and approach, followed by the details of the performed research activities and suggestion for the future work. It is well known that according to current knowledge the pyroprocessing of spent nuclear fuels invariably leads to the dendritic form of electrodeposits, which from technological point of view is undesirable for many reasons. The aim of this research was to study and preclude the formation of electrodeposits with dendritic morphology (of essential importance to FC-1 Program). This project is characterized with four novel study categories: (1) exploring electrodeposit morphology control by controlling the electrochemical deposition reaction rate, (2) the use of rotating disk electrode technique to distinguish the electrodeposition control modes (reaction rate vs. diffusion), (3) morphology studies of lanthanides (La) and actinides (U) in characteristic stages of nucleation and growth, (4) exploring the need for separation of electrochemical cell in compartments for cathodic and anodic reactions. All these study categories were applied on two distinct electrolyte systems (a) high temperature ionic liquids, i.e. molten LiCl-KCl salts, and (b) room temperature ionic liquids (compounds exclusively made of organic cations, and organic/inorganic anions). Because the quality (dense and smooth) of electrodeposits is a direct function of the electrochemical reduction rate (slower the better), the major expectation was that addition of organic molecules would provide the desired slowing down of electroreduction effect, avoiding the undesired dependence on mass transfer. What was learned is summarized in seven key areas.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Protocol for Screening Water Oxidation or Reduction Electrocatalyst Activity in a Three-Electrode Cell for Alkaline Exchange Membrane Electrolysis

Accurate and reproducible screening of the electrocatalytic activity of novel materials for Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) requires establishing an easily adoptable harmonized testing protocol. Herein, we describe a robust, instrumentation-independent testing technique utilizing a three-electrode cell with a fully immersed working electrode. Compared to rotating disk electrode (RDE) techniques, this protocol produces current densities close to those obtained in real electrolyzers and eliminates the usage of the expensive RDE apparatus.

08 HYDROGEN↗

Porous transport electrodes for oxygen evolution reaction in proton exchange membrane water electrolysis -cells: Materials, designs, and diagnoses

H 2 production using proton exchange membrane (PEM) water electrolysis (PEMWE) cells has received considerable attention because of the high efficiencies of these cells and no harmful emissions from the related process. In PEMWE cells, porous transport electrodes (PTEs) composed of a catalyst layer (CL) comprising O 2 evolution reaction (OER) catalysts, porous transport layer (PTL), and PEM play key roles in the stack performance and lifetime. Herein, Ir-based and non-precious-metal OER catalysts that are highly active and stable at low pH values and high anodic potentials are reviewed to understand their OER mechanisms. Various strategies are proposed for engineering CLs and PTLs to improve the interfacial properties and mass transfers of reactants and products to and from the active sites. Additionally, diagnoses of PTEs is significantly crucial for interpreting electrochemical processes and addressing their current challenges. Therefore, half-cell analyses, including diffusion electrode (DE), floating electrode (FE), and modified rotating disk electrode (MRDE) techniques, are explored, and membrane electrode assembly (MEA)-based analyses, such as the polarization technique, electrochemical impedance spectroscopy, and magnetic field analysis, are established. In conclusion, this study aims to provide an overview of recent technologies used for the engineering and diagnostic tools of PEMWE cells and insights into the advanced components and systems to be developed in this field.

Diagnosis of PEMWE Cells↗

Electrocatalysis of fuel cell reactions: Investigation of alternate electrolytes

Oxygen reduction and transport properties of the electrolyte in the phosphoric acid fuel cell are studied. The areas covered were: (1) development of a theoretical expression for the rotating ring disk electrode technique; (2) determination of the intermediate reaction rate constants for oxygen reduction on platinum in phosphoric acid electrolyte; (3) determination of oxygen reduction mechanism in trifluoreomethanesulfonic acid (TFMSA) which was considered as an alternate electrolyte for the acid fuel cells; and (4) the measurement of transport properties of the phosphoric acid electrolyte at high concentrations and temperatures.

Chin, D. T.↗

Quantification of Reactive Oxygen Species Produced from Electrocatalytic Materials

Oxygen electrochemistry goes beyond O 2 , as the formation of reactive oxygen species (ROS) such as H 2 O 2 and O 3 during water oxidation is key in the destruction of persistent pollutants in water remediation technologies as well as in the degradation of fuel cell and electrolyzer components. In this study, we developed an in situ method utilizing the rotating ring-disk electrode technique to quantify the formation of O 2 , O 3 , and H 2 O 2 species across a broad pH range (1–8.3). Oxygen selectivity trends over Pt, IrO 2 , and PbO 2 surfaces reveal that even O 2 evolution catalysts may produce small yet measurable amounts of ROS, further modulated by pH and electrode potential. In conclusion, these findings emphasize the need to probe the selectivity of oxygen electrochemistry for a more complete picture of advanced materials for electrochemical technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalysis of fuel cell reactions: Investigation of alternate electrolytes

Oxygen reduction and transport properties of the electrolyte in the phosphoric acid fuel cell are studied. A theoretical expression for the rotating ring-disk electrode technique; the intermediate reaction rate constants for oxygen reduction on platinum in phosphoric acid electrolyte; oxygen reduction mechanism in trifluoromethanesulfonic acid (TFMSA), considered as an alternate electrolyte for the acid fuel cells; and transport properties of the phosphoric acid electrolyte at high concentrations and temperatures are covered.

Chin, D. T.↗

Anodic Hydrogen Generation from Benzaldehyde on Au, Ag, and Cu: Rotating Ring-Disk Electrode Studies

Aldehydes are selectively oxidized to carboxylates on group 11 metals at low potentials (<0.4 V vs. RHE) in alkaline media. This process can occur by a pathway that generates H 2 gas from the aldehyde, known as electro-oxidative dehydrogenation (EOD) or anodic hydrogen production. The EOD process occurs with transfer of only one electron per aldehyde, whereas typical oxidation with discharge of hydrogen to form water is a two-electron process. Here, we study the catalytic activity and selectivity toward H 2 of Au, Ag, and Cu electrodes using benzaldehyde with rotating disk and ring-disk electrode (RDE/RRDE) techniques. The average number of electrons per benzaldehyde molecule obtained via H 2 detection by RRDE agrees with that obtained via Koutecký-Levich analysis conducted at various rotation rates. We find that Au and Ag have much higher H 2 and benzoate formation rates than Cu, but that Cu can perform the reaction at about 0.2 V lower overpotentials. On all three materials, benzaldehyde oxidation has high selectivity to anodic H 2 (one-electron pathway) below ∼0.5 V vs. RHE, but, with increasing potential, the selectivity shifts to H-oxidation forming water (two-electron pathway).

Ramos, Nathanael C. (ORCID:0000000247210350)↗

Electromagnetic studies of redox systems for energy storage

Both chromium and iron couples were studied on various electrode surfaces in acidic perchlorate solution by using rotating ring-disk techniques. It was found that chloride which forms inner sphere coordination complexes with the redox species enhances the electrode kinetics dramatically. The effects of lead underpotential deposition and surface alloy formation on the kinetics of the chromium couple on gold were studied using both linear sweep voltammetry and potential step techniques. The lad underpotential deposition was found to slow down the kinetics of the reduction of the Cr species on gold surfaces although increase the hydrogen overvoltage. The effect on the chromium kinetics can be explained in terms of principally a double layer effect. The underpotential deposition lead species with its positive charge results in a decrease in the concentration of the Cr species at the electrode surface. Similar phenomena were also observed with bismuth underpotential deposition on gold for the iron couple.

Wu, C. D.↗

Manufacturing Process of Electrode Films

Rotating disk electrode (RDE) experiments form a key experimental characterization technique for measuring electrocatalyst performance and durability. While standard RDE testing protocols have been documented, it has been noted that catalyst film quality can skew measurements. Furthermore, the impact of relative humidity on drying is studied in an effort to produce consistent, high quality catalyst films for RDE experiments, which shows that high quality catalyst films can be manufactured repeatedly in a controlled environment, such as inside an environmental chamber as described.

08 HYDROGEN↗

Ion Storage Tests with the High Performance Antimatter Trap (HiPAT)

The NASA/Marshall Space Flight Centers (NASA/MSFC) Propulsion Research Center (PRC) is evaluating an antiproton storage system, referred to as the High Performance Antiproton Trap (HiPAT). This interest stems from the sheer energy represented by matter/antimatter annihilation process with has an energy density approximately 10 order of magnitude above that of chemical propellants. In other terms, one gram of antiprotons contains the equivalent energy of approximately 23 space shuttle external tanks or ET's (each ET contains roughly 740,000 kgs of fuel and oxidizer). This incredible source of stored energy, if harnessed, would be an enabling technology for deep space mission where both spacecraft weight and propulsion performance are key to satisfying aggressive mission requirements. The HiPAT hardware consists of a 4 Tesla superconductor system, an ultra high vacuum test section (vacuum approaching 10(exp -12) torr), and a high voltage confinement electrode system (up to 20 kvolts operation). The current laboratory layout is illustrated. The HiPAT designed objectives included storage of up to 1 trillion antiprotons with corresponding lifetimes approaching 18 days. To date, testing has centered on the storage of positive hydrogen ions produced in situ by a stream of high-energy electrons that passes through the trapping region. However, due to space charge issues and electron beam compression as it passes through the HiPAT central field, current ion production is limited to less then 50,000 ions. Ion lifetime was determined by counting particle populations at the end of various storage time intervals. Particle detection was accomplished by destructively expelling the ions against a micro-channel plate located just outside the traps magnetic field. The effect of radio frequency (RF) stabilization on the lifetime of trapped particles was also examined. This technique, referred to as a rotating wall, made use of a segmented electrode located near the center of the trap on which various phases of a particular frequency were applied. Various experiments were performed illustrating the ability of an RF drive to both prolong and reduced the lifetimes of various ion species depending on the selected frequency. HiPAT is now being reconfigured for testing with an ion source that will provide both positive and negative hydrogen ions from an external source. This ion system shall provide higher fill capacity (order of million of ions per shot), stacking of multiple shots, and injection schemes typical of a realistic antiproton delivery system.

Martin, James J.↗

Rotating Drive for Electrical-Arc Machining

Rotating drive improves quality of holes made by electrical-arc machining. Mechanism (Uni-tek, rotary head, or equivalent) attached to electrical-arc system. Drive rotates electrode as though it were mechanical drill, while an arc disintegrates metal in workpiece, thereby creating hole. Rotating electrode method often used in electric-discharge machining. NASA innovation is application of technique to electrical-arc machining.

Fransen, C. D.↗

Precise micromotion compensation of a tilted ion chain

Excess micromotion can be a substantial source of errors in trapped-ion based quantum processors and clocks due to the sensitivity of the internal states of the ion to external fields and motion. This problem can be fixed by compensating background electric fields in order to position ions at the RF node and minimize their driven micromotion. Here we describe techniques for compensating ion chains in scalable surface ion traps. These traps are capable of cancelling stray electric fields with fine spatial resolution in order to compensate multiple closely spaced ions due to their large number of relatively small control electrodes. We demonstrate a technique that compensates an ion chain to better than 5 V/m and within 0.1 degrees of chain rotation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Convergence of limb, visceral, and vertical semicircular canal or otolith inputs onto vestibular nucleus neurons

The major goal of this study was to determine the patterns of convergence of non-labyrinthine inputs from the limbs and viscera onto vestibular nucleus neurons receiving signals from vertical semicircular canals or otolith organs. A secondary aim was to ascertain whether the effects of non-labyrinthine inputs on the activity of vestibular nucleus neurons is affected by bilateral peripheral vestibular lesions. The majority (72%) of vestibular nucleus neurons in labyrinth-intact animals whose firing was modulated by vertical rotations responded to electrical stimulation of limb and/or visceral nerves. The activity of even more vestibular nucleus neurons (93%) was affected by limb or visceral nerve stimulation in chronically labyrinthectomized preparations. Some neurons received non-labyrinthine inputs from a variety of peripheral sources, including antagonist muscles acting at the same joint, whereas others received inputs from more limited sources. There was no apparent relationship between the spatial and dynamic properties of a neuron's responses to tilts in vertical planes and the non-labyrinthine inputs that it received. These data suggest that non-labyrinthine inputs elicited during movement will modulate the processing of information by the central vestibular system, and may contribute to the recovery of spontaneous activity of vestibular nucleus neurons following peripheral vestibular lesions. Furthermore, some vestibular nucleus neurons with non-labyrinthine inputs may be activated only during particular behaviors that elicit a specific combination of limb and visceral inputs.

NASA Discipline Developmental Biology↗

HIGH VOLTAGE DESIGN AND EVALUATION OF WIEN FILTERS FOR THE CEBAF 200 keV INJECTOR UPGRADE

High-energy nuclear physics experiments at the Jefferson Lab Continuous Electron Beam Accelerator Facility (CEBAF) require highly spin-polarization electron beams, produced from strained super-lattice GaAs photocathodes, activated to negative electron affinity in a photogun operating at 130 kV dc. A pair of Wien filter spin rotators in the injector defines the orientation of the electron beam polarization at the end station target. An upgrade of the CEBAF injector to better support the upcoming MOLLER experiment requires increasing the electron beam energy to 200 keV, to reduce unwanted helicity correlated intensity and position systematics and provide precise control of the polarization orientation. Our contribution describes design, fabrication and testing of the high voltage system to upgrade the Wien spin rotator to be compatible with the 200 keV beam. This required Solidworks modeling, CST and Opera electro- and magnetostatic simulations, upgrading HV vacuum feedthroughs, and assembly techniques for improving electrode alignment. The electric and magnetic fields required by the Wien condition and the successful HV characterization under vacuum conditions are also presented.

Palacios-Serrano, G.↗

Machine learning-based ethylene and carbon monoxide estimation, real-time optimization, and multivariable feedback control of an experimental electrochemical reactor

Electrochemical reduction of CO 2 gas is a novel CO 2 utilization technique that has the potential to mitigate the global climate crisis caused by anthropogenic CO 2 emissions, and enable the large-scale storage of energy generated from renewable sources in the form of carbon-based chemicals and fuels. However, due to the complexity of the electrochemical reactions, the explicit first-principles models for CO2 reduction are not available yet, and there has been a limited effort to develop process modeling, optimization and control of CO 2 electrochemical reactors. To this end, a rotating cylinder electrode (RCE) reactor has been constructed at UCLA to understand the mass transfer and reaction kinetics effects separately on the productivity. In the RCE reactor, the applied potential strongly influences the reaction energetics and the electrode rotation speed affects the hydrodynamic boundary layer and modifies the film mass transfer coefficient, which involves convective and diffusive transport. Further, the present work aims to develop a multi-input multi-output (MIMO) control scheme for the RCE reactor that integrates techniques from artificial and recurrent neural network modeling, nonlinear optimization, and process controller design. Specifically, production rates of two products from the experimental reactor, ethylene and carbon monoxide, are controlled by manipulating two inputs, applied potential and catalyst rotation speed. Process dynamics and controllability are analyzed, a feedback control strategy is designed and the controllers are tuned accordingly. The experimental electrochemical cell is employed to gather data for process modeling and implement the multivariable control system. Finally, the experimental results are presented which demonstrate excellent closed-loop performance by the control system and regulation of the outputs at three different set-points including an economically-optimal set-point.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational problems in autoregressive moving average (ARMA) models

The choice of the sampling interval and the selection of the order of the model in time series analysis are considered. Band limited (up to 15 Hz) random torque perturbations are applied to the human ankle joint. The applied torque input, the angular rotation output, and the electromyographic activity using surface electrodes from the extensor and flexor muscles of the ankle joint are recorded. Autoregressive moving average models are developed. A parameter constraining technique is applied to develop more reliable models. The asymptotic behavior of the system must be taken into account during parameter optimization to develop predictive models.

Agarwal, G. C.↗