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NASA NTRS2017

Highly Reducing Partitioning Experiments Relevant to the Planet Mercury

With the data returned from the MErcury Surface Space ENvironment GEochemistry and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high S and low FeO contents observed from MESSENGER on the planet's surface suggests a low oxygen fugacity of the present planetary materials. Estimates of the oxygen fugacity for Mercurian magmas are approximately 3-7 log units below the Iron-Wüstite (Fe-FeO) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from such as the Earth, Moon, or Mars. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions are available in our collections (e.g., enstatite chondrites, achondrites, aubrites). With this limited amount of material, we must perform experiments to determine the elemental partitioning behavior of typically lithophile elements as a function of decreasing oxygen fugacity. Experiments are being conducted at 4 GPa in an 880-ton multi-anvil press, at temperatures up to 1850degC. The composition of starting materials for the experiments were selected for the final run products to contain metal, silicate melt, and sulfide melt phases. Oxygen fugacity is controlled in the experiments by adding silicon metal to the samples, using the Si-SiO2 oxygen buffer, which is approximately 5 log units more reducing than the Fe-FeO oxygen buffer at our temperatures of interest. The target silicate melt compositional is diopside (CaMgSi2O6) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. Elements detected on Mercury's surface by MESSENGER (K, Na, Fe, Ti, Cl, Al, Cr, Mn, U, Th) and other geochemically relevant elements (P, F, H, N, C, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb) are added to the starting composition at trace abundances (approximately 500 ppm) so that they are close enough to infinite dilution to follow Henry's law of trace elements, and their partitioning behavior can be measured between the metal, silicate, and sulfide phases. The results of these experiments will allow us to assess the thermal and magmatic evolution of the planet Mercury from a geochemical standpoint.

Rowland, Rick, II↗
NASA NTRS2010

Proceedings of the Astrobiology Science Conference 2010. Evolution and Life: Surviving Catastrophes and Extremes on Earth and Beyond

The Program of the 2010 Astrobiology Science Conference: Evolution and Life: Surviving Catastrophes and Extremes on Earth and Beyond, included sessions on: 50 Years of Exobiology and Astrobiology: Greatest Hits; Extraterrestrial Molecular Evolution and Pre-Biological Chemistry: From the Interstellar Medium to the Solar System I; Human Exploration, Astronaut Health; Diversity in Astrobiology Research and Education; Titan: Past, Present, and Future; Energy Flow in Microbial Ecosystems; Extraterrestrial Molecular Evolution and Prebiological Chemistry: From the Interstellar Medium to the Solar System II; Astrobiology in Orbit; Astrobiology and Interdisciplinary Communication; Science from Rio Tinto: An Acidic Environment; Can We Rule Out Spontaneous Generation of RNA as the Key Step in the Origin of Life?; How Hellish Was the Hadean Earth?; Results from ASTEP and Other Astrobiology Field Campaigns I; Prebiotic Evolution: From Chemistry to Life I; Adaptation of Life in Hostile Space Environments; Extrasolar Terrestrial Planets I: Formation and Composition; Collaborative Tools and Technology for Astrobiology; Results from ASTEP and Other Astrobiology Field Campaigns II; Prebiotic Evolution: From Chemistry to Life II; Survival, Growth, and Evolution of Microrganisms in Model Extraterrestrial Environments; Extrasolar Terrestrial Planets II: Habitability and Life; Planetary Science Decadal Survey Update; Astrobiology Research Funding; Bioessential Elements Through Space and Time I; State of the Art in Life Detection; Terrestrial Evolution: Implications for the Past, Present, and Future of Life on Earth; Psychrophiles and Polar Environments; Life in Volcanic Environments: On Earth and Beyond; Geochronology and Astrobiology On and Off the Earth; Bioessential Elements Through Space and Time II; Origins and Evolution of Genetic Systems; Evolution of Advanced Life; Water-rich Asteroids and Moons: Composition and Astrobiological Potential; Impact Events and Evolution; A Warm, Wet Mars?; Titan Versus Europa - Potential for Astrobiology; Habitability Potential of Mars; Biosignatures: Tools and Development I; Origins of Molecular Asymmetry, Homochirality, and Life Detection; Deserts and Evaporite Basins and Associated Microbialite Systems; Ancient Life and Synthetic Biology: Crossroad of the Past and Future; Biosignatures: Tools and Development II; Free Oxygen: Proxies, Causes, and Consequences; Life in Modern Microbialite Systems - Function and Adaptation; Hydrothermal Systems and Organosynthesis Processes: Origin and Evolution of Life; Where Should We Go on Mars to Seek Signs of Life?; Search for Intelligent Life I. Innovative SETI Observing Programs and Future Directions; Integrating Astrobiology Research Across and Beyond the Community; Education in Astrobiology in K-12; Search for Intelligent Life II. Global Engagement and Interstellar Message Construction; Poster sessions included: Extraterrestrial Molecular Evolution and Pre-Biological Chemistry; Prebiotic Evolution: From Chemistry to Life; RNA World; Terrestrial Evolution: Implications for the Past, Present, and Future of Life on Earth; Hydrothermal Systems and Organosynthesis Processes: Origin and Evolution of Life; Virology and Astrobiology; Horizontal Genetic Transfer and Properties of Ancestral Organisms; Life in Volcanic Environments: On Earth and Beyond; Impact Events and Evolution; Evolution of Advanced Life; Evolution of Intelligent Life; Education in Astrobiology in K-12; Origins of Molecular Asymmetry, Homochirality, and Life Detection; Astrobiology and Interdisciplinary Communication; Diversity in Astrobiology Research and Education; Integrating Astrobiology Research Across and Beyond the Community; Policy and Societal Issues: Dealing with Potential Bumps in the Astrobiology Road Ahead; Results from ASTEP and Other Astrobiology Field Campaigns; Energy Flow in Microbial Ecosystems; Psychrophiles and Polar Environments; Deserts and Evaporite Basins and Associated Microbialite stems; Life in Modern Microbialite Systems - Function and Adaptation; Free Oxygen: Proxies, Causes, and Consequences; Bioessential Elements Through Space and Time; Water-rich Asteroids and Moons: Composition and Astrobiological Potential; Biosignatures: Tools and Developments; Robotics and Instrumentation for Astrobiology; State of the Art in Life Detection; Astrobiology in Orbit; Survival, Growth, and Evolution of Microrganisms in Model Extraterrestrial Evolution; Search for Intelligent Life; Habitability Potential of Mars; How and Where Should We Seek Signs of Life on Mars?; Titan: Past, Present, and Future; Extrasolar Terrestrial Planets: Formation, Composition, Diversity, Habitability and Life; Human Exploration, Astronaut Health; Science from Rio Tinto: An Acidic Environment and Adaptation of Life in Hostile Space Environments;

Source record↗
NASA NTRS2017

Assessing the Behavior of Typically Lithophile Elements Under Highly Reducing Conditions Relevant to the Planet Mercury

With the data returned from the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition (e.g., Evans et al. 2012; Nittler et al. 201 l; Peplowski et al. 2012; Weider et al. 2012). The high Sand low FeO contents observed from MESSENGER on the planet's surface suggests a low oxygen fugacity of the present planetary materials. Estimates of the oxygen fugacity for Mercurian magmas are approximately 3- 7 log units below the Iron-Wiistite (Fe-FeO) oxygen buffer (McCubbin et al. 2012; Zolotov et al. 2013), several orders of magnitude more reducing than other terrestrial bodies we have data from such as the Earth, Moon, or Mars (Herd 2008; Sharp, McCubbin, and Shearer 2013; Wadhwa 2008). Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions are available in our collections (e.g., enstatite chondrites, achondrites, aubrites). The goal of this study is to conduct experiments at high pressure and temperature conditions to determine the elemental partitioning behavior of typically lithophile elements as a function of decreasing oxygen fugacity.

Rowland, Rick, II↗
NASA NTRS1972

Photodissociation rates of molecular oxygen in the mesosphere and lower thermosphere.

Use of recently obtained band oscillator strengths and predissociation line widths, for the Schumann-Runge band system to calculate the photodissociation rate of molecular oxygen as a function of column density and temperature by solar radiation between 1025 and 2500 A. Data are presented from which the mean transmission and photodissociation rates for given wavelength intervals between 1750 and 2025 A can be calculated for column densities between 10 to the 17th and 10 to the 23rd molecules/sq cm and for temperatures between 150 and 300 K. Also, the production of vibrationally excited oxygen molecules as a result of fluorescence in the Schumann-Runge bands is discussed.

Hudson, R. D.↗
DOE OSTI2021

Air separation via a two-step solar thermochemical cycle based on (Ba,La) x Sr 1-x FeO 3-δ : Thermodynamic analysis

A two-step solar thermochemical cycle was considered for air separation to produce N2 based on (Ba,La) x Sr 1-x FeO 3-δ perovskite reduction/oxidation (redox) reactions for A-site fractions of 0 ≤ x ≤ 0.2. The cycle steps encompassed (1) thermal reduction and O 2 release via concentrated solar input and (2) re-oxidation with air to uptake O 2 and produce high-purity N 2 . Thermogravimetry at temperatures between 400 and 1100 °C in atmospheres of 0.005 to 90% O 2 /Ar at 1 bar was performed to measure equilibrium nonstoichiometries. The compound energy formalism was applied to model redox thermodynamics for both Ba 2+ and La 3+ substitution. Non-linear regression was used to determine the empirical parameters based on the thermogravimetric measurements. The model was used to define partial molar reaction enthalpies and entropies and predicted equilibrium oxygen nonstoichiometry as functions of oxide stoichiometry, site fraction, temperature, and O 2 partial pressure. The thermodynamic analysis showed the materials are appealing for air separation at temperatures below 800 °C.

42 ENGINEERING↗
DOE OSTI2023

Resolving Diverse Oxygen Transport Pathways Across Sr‐Doped Lanthanum Ferrite and Metal‐Perovskite Heterostructures

Abstract Perovskite structured transition metal oxides are important technological materials for catalysis and solid oxide fuel cell applications. Their functionality often depends on oxygen diffusivity and mobility through complex oxide heterostructures, which can be significantly impacted by structural and chemical modifications, such as doping. Further, when utilized within electrochemical cells, interfacial reactions with other components (e.g., Ni‐ and Cr‐based alloy electrodes and interconnects) can influence the perovskite's reactivity and ion transport, leading to complex dependencies that are difficult to control in real‐world environments. Here, this work uses isotopic tracers and atom probe tomography to directly visualize oxygen diffusion and transport pathways across perovskite and metal‐perovskite heterostructures, that is, (Ni‐Cr coated) Sr‐doped lanthanum ferrite (La 0.5 Sr 0.5 FeO 3 ; LSFO). Annealing in 18 O 2(g) results in elemental and isotopic redistributions through oxygen exchange (OE) in the LSFO while Ni‐Cr undergoes oxidation via multiple mechanisms and transport pathways. Complementary density functional theory calculations at experimental conditions provide rationale for OE reaction mechanisms and reveal a complex interplay of different thermodynamic and kinetic drivers. These results shed light on the fundamental coupling of defects and oxygen transport in an important class of catalytic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Tuning the surface reactivity of oxides by peroxide species

The Mars–van Krevelen mechanism is the foundation for oxide-catalyzed oxidation reactions and relies on spatiotemporally separated redox steps. Herein, we demonstrate the tunability of this separation with peroxide species formed by excessively adsorbed oxygen, thereby modifying the catalytic activity and selectivity of the oxide. Using CuO as an example, we show that a surface layer of peroxide species acts as a promotor to significantly enhance CuO reducibility in favor of H 2 oxidation but conversely as an inhibitor to suppress CuO reduction against CO oxidation. Together with atomistic modeling, we identify that this opposite effect of the peroxide on the two oxidation reactions stems from its modification on coordinately unsaturated sites of the oxide surface. By differentiating the chemical functionality between lattice oxygen and peroxide, these results are closely relevant to a wide range of catalytic oxidation reactions using excessively adsorbed oxygen to activate lattice oxygen and tune the activity and selectivity of redox sites.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Quantification of Dissolved O 2 in Bulk Aqueous Solutions and Porous Media Using NMR Relaxometry

Effects of dissolved paramagnetic oxygen (O 2 ) in water on 1 H nuclear magnetic resonance (NMR) Carr-Purcell-Meiboom-Gill (CPMG) experiments is evaluated at a 1 H Larmor frequency of 2 MHz. Dissolution of O 2 into water significantly reduces the 1 H transverse relaxation coefficient (T 2 ). For deoxygenated water, T 2 is 3388 ms, water at ambient atmospheric conditions (7.4 mg/L O2) exhibits a T2 of 2465 ms, and dissolution of 2710 mg/L O 2 further reduces T 2 to 36 ms. The results were fit with an empirical model to facilitate prediction of T 2 times for bulk water as a function of paramagnetic oxygen concentrations in solution. Dissolved O 2 also greatly influences 1 H NMR CPMG experiments of confined water in a model system composed of Berea sandstone. For this system, 90 mg/L O 2 in H 2 O enhances T 2 relaxation of bulk water such that the relaxation time is comparable to physically confined water in the sandstone pores. Given the sensitivity of NMR T 2 coefficients to paramagnetic oxygen, low-field NMR-based characterization of fluid and porous media structure requires control of dissolved oxygen, as geospatial variation in the partial pressure of O 2 alone is expected to perturb fluid and pore relaxation times by up to 60 and 36%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2007

Radio Frequency Mass Gauging of Propellants

A combined experimental and computer simulation effort was conducted to measure radio frequency (RF) tank resonance modes in a dewar partially filled with liquid oxygen, and compare the measurements with numerical simulations. The goal of the effort was to demonstrate that computer simulations of a tank's electromagnetic eigenmodes can be used to accurately predict ground-based measurements, thereby providing a computational tool for predicting tank modes in a low-gravity environment. Matching the measured resonant frequencies of several tank modes with computer simulations can be used to gauge the amount of liquid in a tank, thus providing a possible method to gauge cryogenic propellant tanks in low-gravity. Using a handheld RF spectrum analyzer and a small antenna in a 46 liter capacity dewar for experimental measurements, we have verified that the four lowest transverse magnetic eigenmodes can be accurately predicted as a function of liquid oxygen fill level using computer simulations. The input to the computer simulations consisted of tank dimensions, and the dielectric constant of the fluid. Without using any adjustable parameters, the calculated and measured frequencies agree such that the liquid oxygen fill level was gauged to within 2 percent full scale uncertainty. These results demonstrate the utility of using electromagnetic simulations to form the basis of an RF mass gauging technology with the power to simulate tank resonance frequencies from arbitrary fluid configurations.

Zimmerli, Gregory A.↗
NASA NTRS1995

Ponderomotive effects on distributions of O(+) ions in the auroral zone

Test particle calculations are used to compute the effects of gravity and ponderomotive acceleration by shear Alfven wave oscillations on the distribution function of O(+) ions along auroral field lines, assuming an ionospheric Maxwellian source of the ions at 2000 km altitude with approximately 0.5 eV of thermal energy in the parallel component of velocity. The electric field model corresponds to a standing wave oscillation with a frequency approximately 1 Hz in the azimuthal direction superimposed on the background dipole field, in which the wave amplitude is either increasing or decreasing in time. The electric field is taken to be primarily in the perpendicular direction. The time varying wave produces broad distributions with widths of 2 to 10 times the initial 0.5-eV thermal energy of the Maxwellian source, and the density and flux of upward going O(+) ions at one Earth radius are both enhanced in this model. The oxygen ion distribution functions at 1 R(sub E) altitude resulting from interaction with waves whose amplitudes are increasing in time have a more gradual lower energy cutoff than do the distribution functions resulting from decaying waves. The high-energy part of the distribution functions in growing waves reflects the temperature of the Maxwellian source, while the high-energy part of the distributions resulting from decaying waves steepens with time, independent of the source temperature.

Witt, E.↗
NASA NTRS2011

Identification of Cardiometabolic Vulnerabilities Caused by Effects of Synergistic Stressors that are Commonly Encountered During Space Missions

Microgravity is a physiologically challenging state even when at rest. Astronauts experience additional physical and mental stresses, such as prolonged exertion, sleep loss and circadian misalignment, that could impact cardiovascular function. The main goals of this four year NASA project are to characterize the independent and synergistic effects on cardiovascular and immune function of: (1) circadian misalignment; (2) sleep loss; and (3) varied physical and mental stressors, mimicking some of the synergistic stressors experienced by astronauts. Sixteen healthy volunteers, aged 35-55 years, will be studied with standardized behavioral stressors occurring across all circadian phases, both with and without accruing sleep loss, achieved via two 11-day "forced desynchrony" protocols performed in each subject (randomized, within-subject design), where wake periods are advanced 4-h each "day" (i.e. recurring 20-h "days"). One protocol permits 8.33 h sleep opportunity per 20-h "day" (=10 h sleep per 24-h), and the other permits 5 h sleep per 20-h "day" (=6 h sleep per 24-h; matching the reported sleep duration of astronauts). In both protocols, subjects will perform a standardized stress battery including a cognitively challenging task; bicycle exercise, and passive 60deg head up tilt. Outcome variables include blood pressure, heart rate, arrhythmia frequency, cardiac vagal tone (from heart rate variability), sympathetic activity (catecholamines), and endothelial function. Additional measures of cardiac function (echocardiography), responses to a passive 80deg head up tilt, maximal oxygen uptake, and immune function will be assessed at the beginning and at the end of each protocol (i.e., without and with sleep loss, and before and after circadian misalignment). We hope to identify the relative impact on cardiovascular risk markers of varied behavioural stressors while subjects experience circadian misalignment and sleep loss, mimicking some of the synergistic stressors experienced by astronauts. Supported by NASANNX1 OAR 1 OG.

Ruger, M.↗
NASA NTRS1985

Distribution and abundance of organic thiols

The role of glutathione (GSH) in protecting against the toxicity of oxygen and oxygen by products is well established for all eukaryotes studied except Entamoeba histolytica which lacks mitochrondria, chloroplasts, and microtubules. The GSH is not universal among prokaryotes. Entamoeba histolytica does not produce GSH or key enzymes of GSH metabolism. A general method of thiol analysis based upon fluorescent labeling with monobromobimane and HPLC separation of the resulting thiol derivatives was developed to determine the occurrence of GSH and other low molecular weight thiols in bacteria. Glutathione is the major thiol in cyanobacteria and in most bacteria closely related to the purple photosynthetic bacteria, but GSH was not found in archaebacteria, green bacteria, or GRAM positive bacteria. It suggested that glutathione metabolism was incorporated into eukaryotes at the time that mitochondria and chloroplasts were acquired by endosymbiosis. In Gram positive aerobes, coenzyme A occurs at millimolar levels and CoA disulfide reductases are identified. The CoA, rather than glutathione, may function in the oxygen detoxification processes of these organisms.

Fahey, R.↗
DOE OSTI2020

Prussian blue analogues as platform materials for understanding and developing oxygen evolution reaction electrocatalysts

Transition metal based materials containing Fe have drawn great attention as oxygen evolution reaction (OER) catalysts. The nature of the electrocatalytic active species remains under debate due to the ambiguous physicochemical properties of the catalyst materials, such as the oxidation states and crystal structures. Here, in order to address this issue, transition metal Prussian blue analogues (TM-PBA, Na(TM)(Fe)(CN) 6 , TM = V, Fe, Co, and Ni) with an isomorphous structure are investigated for OER catalysis. Our combined experimental measurements and density functional theory (DFT) calculations reveal that TM-PBAs exhibit volcano-like OER activity with Ni-PBA located near the top of the volcano. Such a volcano-like activity profile can be attributed to the distinctive binding energy difference between *O and *OH on different TM-PBAs surfaces. This research demonstrates that TM-PBAs can be used as platform materials for understanding structure-property-activity relationships in OER catalysts.

25 ENERGY STORAGE↗
DOE OSTI2021

Reduction Thermodynamics of Sr 1– x Ce x MnO 3 and Ce x Sr 2– x MnO 4 Perovskites for Solar Thermochemical Hydrogen Production

Herein, the compositional families Sr 1–x Ce x MnO 3 (SCMX, X = 100x, x = 0.10, 0.20, and 0.30) and Ce x Sr 2–x MnO 4 (CSMX, X = 100x, x = 0.10, 0.20, and 0.30) are studied to determine the effects of perovskite structure and cerium content on thermal reduction thermodynamics and the resulting impact on solar thermochemical hydrogen production (STCH). Relying on thermogravimetric results from oxygen nonstoichiometry experiments, fits for various thermodynamic quantities are produced, including defect-reaction specific enthalpy (Δ H) and entropy (Δ S ), as well as the δ-dependent standard partial molar enthalpy, Δh¯$^{°}_{Ο}$, and entropy Δs¯$^{°}_{Ο}$, of oxygen as a function of composition within these two perovskite families. Here, the results of this thermodynamic study are also discussed in the context of structure and cerium dopant level. Experimental hydrogen production results show that the SCM family produces slightly larger amounts of hydrogen per mole of oxide compared with the CSM family under similar reduction and oxidation temperature conditions, however, a direct correlation between structure, cerium content, and water-splitting capacity could not be discerned.

08 HYDROGEN↗
DOE OSTI2022

Effect of porous transport layer properties on the anode electrode in anion exchange membrane electrolyzers

Anion exchange membrane water electrolyzers (AEMELs) have recently received significant attention due to their potential advantages over existing commercial water electrolysis technologies. However, AEM electrolyzers have not yet met performance and durability targets. One of the critical components in achieving high AEMEL performance is the porous transport layer (PTL) which serves many critical functions in the oxygen evolution reaction (OER) electrode. In this study, several OER PTL attributes were investigated, including: material of construction, fabrication method, feature size, porosity/density, and thickness. It was found that higher porosity helped facilitate multiphase (O 2 , H 2 O, etc.) transport; however, as the porosity increased, the catalyst layer adhesion to the PTL decreased, the contact resistance with the bipolar plate increased and the cell operating voltage increased. It was found that nickel-based PTLs allowed for lower operating voltages than similarly-structured stainless steel PTLs. Improved operating voltages were achieved with both fiber felts and sintered structures by porosity optimization. Furthermore, an increase in thickness did not affect transient voltage response, however, it had a negative effect on performance stability. As a result, the experimental findings presented here provide important insights for development of PTL materials and structures for efficient and low-cost water electrolysis.

08 HYDROGEN↗
DOE OSTI2020

Mechanism of Chlorine-Mediated Electrochemical Ethylene Oxidation in Saline Water

Chlorine as a redox mediator allows for the selective oxidation of ethylene to 2-chloroethanol, which converts to ethylene oxide in alkaline aqueous electrolyte. This strategy utilizes abundant saline water as an electrolyte and source of oxygen atoms for functionalization. We present a mechanistic study of ethylene oxidation in saline water using cobalt oxide nanoparticle catalysts. Electrochemical kinetic analysis and in situ X-ray absorption spectroscopy suggest that the resting state of the catalyst and the rate-determining step differ for the chlorine evolution reaction in the presence and absence of ethylene. In 0.6 M NaCl pH 8 electrolyte, which resembles seawater, the average current density was ~60 mA/cm 2 with a Faradaic efficiency of ~41% toward ethylene functionalization. The use of synthetic and natural seawater achieved Faradaic efficiencies above 70%, while the partial current toward the product remained invariant. Further conversion of the initial product 2-chloroethanol into ethylene glycol was also demonstrated. Here, we present a broader vision of harnessing saline water in electrochemical functionalization of organic molecules and coproduction of hydrogen.

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

Energy-Efficient Capacitive Deionization through Electrode Modification and Process Development

Electrochemical separation technologies, such as capacitive deionization (CDI), are promising for addressing global energy and water challenges. However, there is a need to improve the performance, better understand property-performance relationships, and evaluate the longevity of CDI electrodes. This study explores the chemical modification of electrodes and the adjustment of CDI operating parameters. Results indicate that nitric acid (HNO3) conditioning of activated carbon cloth (ACC) electrodes removes metal oxides, introduces oxygen and nitrogen functionalities, and increases the specific capacitance (16% at 1 mV/s). Moreover, these changes in electrode properties positively impact device-level CDI performance. Through HNO3-conditioning of the ACC and tuning of the operational parameters, this work demonstrates higher electrosorption capacity (4.0x), greater charge efficiency (90% vs 24%), and lower energy consumption (3.8x). Despite these enhancements, limitations of the HNO 3 -conditioned ACC include decreased desorption kinetics and a 32% loss in electrosorption capacity after 200 cycles. Overall, this work provides guidance on using oxidative pretreatment via HNO 3 to modify ACC electrodes for CDI and evaluates the trade-offs associated with varying operational parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Reversible Emulsions from Polyoxometalate–Polymer: A Robust Strategy to Cyclic Emulsion Catalysis and High-Internal-Phase Emulsion Materials

Reversible Pickering emulsions, achieved by switchable, interfacially active colloidal particles, that enable on-demand emulsification/demulsification or phase inversion, hold substantial promise for biphasic catalysis, emulsion polymerization, cutting fluids, and crude oil pipeline transportation. However, particles with such a responsive behavior usually require complex chemical syntheses and surface modifications, limiting their extensive use. Herein, we report a simple route to generate emulsions that can be controlled and reversibly undergo phase inversion. The emulsions are prepared and stabilized by the interfacial assembly of polyoxometalate (POM)–polymer, where their electrostatic interaction at the interface is dynamic. The wettability of the POMs that dictates the emulsion type can be readily regulated by tuning the number of polymer chains bound to POMs, which, in turn, can be controlled by varying the concentrations of both components and the water/oil ratio. In addition, the number of polymer chains anchored to the POMs can be varied by controlling the number of negative charges on the POMs through an in situ redox reaction. As such, a reversible inversion of the emulsions can be triggered by switching between exposure to ultraviolet light and the introduction of oxygen. Combining the functions of POM itself, a cyclic interfacial catalysis system was realized. Inversion of the emulsion also affords a pathway to high-internal-phase emulsions. Finally, the diversity of the POMs, the polymers, and the responsive switching groups open numerous new, simple strategies for designing a wide range of responsive soft matter for cargo loading, controlled release, and delivery in biomedical and engineering applications without time-consuming particle syntheses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗