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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Inhibition of d-xylose isomerase by polyols: atomic details by joint X-ray/neutron crystallography

A joint X-ray/neutron structure of d-xylose isomerase in complex with the inhibitor sorbitol was determined at room temperature at an acidic pH of 5.9. Protonation of the O5 O atom of the sugar was directly observed in the nuclear density maps. Under acidic conditions sorbitol gains a water-mediated interaction with the enzyme active site, which may explain the increased potency of the inhibitor at low pH. d-Xylose isomerase (XI) converts the aldo-sugars xylose and glucose to their keto analogs xylulose and fructose, but is strongly inhibited by the polyols xylitol and sorbitol, especially at acidic pH. In order to understand the atomic details of polyol binding to the XI active site, a 2.0 Å resolution room-temperature joint X-ray/neutron structure of XI in complex with Ni{sup 2+} cofactors and sorbitol inhibitor at pH 5.9 and a room-temperature X-ray structure of XI containing Mg{sup 2+} ions and xylitol at the physiological pH of 7.7 were obtained. The protonation of oxygen O5 of the inhibitor, which was found to be deprotonated and negatively charged in previous structures of XI complexed with linear glucose and xylulose, was directly observed. The Ni{sup 2+} ions occupying the catalytic metal site (M2) were found at two locations, while Mg{sup 2+} in M2 is very mobile and has a high B factor. Under acidic conditions sorbitol gains a water-mediated interaction that connects its O1 hydroxyl to Asp257. This contact is not found in structures at basic pH. The new interaction that is formed may improve the binding of the inhibitor, providing an explanation for the increased affinity of the polyols for XI at low pH.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Water-soluble drug partitioning and adsorption in HEMA/MAA hydrogels

Two-photon confocal microscopy and back extraction with UV/Vis-absorption spectrophotometry quantify equilibrium partition coefficients, k, for six prototypical drugs in five soft-contact-lens-material hydrogels over a range of water contents from 40 to 92%. Partition coefficients were obtained for acetazolamide, caffeine, hydrocortisone, Oregon Green 488, sodium fluorescein, and theophylline in 2-hydroxyethyl methacrylate/methacrylic acid (HEMA/MAA, pK a ≈ 5.2) copolymer hydrogels as functions of composition, aqueous pH (2 and 7.4), and salinity. At pH 2, the hydrogels are nonionic, whereas at pH 7.4, hydrogels are anionic due to MAA ionization. Solute adsorption on and nonspecific electrostatic interaction with the polymer matrix are pronounced. To express deviation from ideal partitioning, we define an enhancement or exclusion factor, E≡k/φ 1 , where φ 1 is hydrogel water volume fraction. All solutes exhibit E>1 in 100wt % HEMA hydrogels owing to strong specific adsorption to HEMA strands. For all solutes, E significantly decreases upon incorporation of anionic MAA into the hydrogel due to lack of adsorption onto charged MAA moieties. For dianionic sodium fluorescein and Oregon Green 488, and partially ionized monoanionic acetazolamide at pH 7.4, however, the decrease in E is more severe than that for similar-sized nonionic solutes. Conversely, at pH 2, E generally increases with addition of the nonionic MAA copolymer due to strong preferential adsorption to the uncharged carboxylic-acid group of MAA. For all cases, we quantitatively predict enhancement factors for the six drugs using only independently obtained parameters. In dilute solution for solute i , E i is conveniently expressed as a product of individual enhancement factors for size exclusion (E$_i^{ex}$), electrostatic interaction (E$_i^{el}$), and specific adsorption (E$_i^{ad}$):E$_i$≡E$_i^{ex}$E$_i^{el}$E$_i^{ad}$. Finally, to obtain the individual enhancement factors, we employ an extended Ogston mesh-size distribution for Eiex; Donnan equilibrium for E$_i^{el}$; and Henry's law characterizing specific adsorption to the polymer chains for E$_i^{ad}$. Predicted enhancement factors are in excellent agreement with experiment.

back extraction↗
DOE OSTI2017

Equilibria model for pH variations and ion adsorption in capacitive deionization electrodes

Ion adsorption and equilibrium between electrolyte and microstructure of porous electrodes are at the heart of capacitive deionization (CDI) research. Surface functional groups are among the factors which fundamentally affect adsorption characteristics of the material and hence CDI system performance in general. Current CDI-based models for surface charge are mainly based on a fixed (constant) charge density, and do not treat acid-base equilibria of electrode microstructure including so-called micropores. Here, we expand current models by coupling the modified Donnan (mD) model with weak electrolyte acid-base equilibria theory. In our model, surface charge density can vary based on equilibrium constants (pK's) of individual surface groups as well as micropore and electrolyte pH environments. In this initial paper, we consider this equilibrium in the absence of Faradaic reactions. The model shows the preferential adsorption of cations versus anions to surfaces with respectively acidic or basic surface functional groups. We introduce a new parameter we term “chemical charge efficiency” to quantify efficiency of salt removal due to surface functional groups. We validate our model using well controlled titration experiments for an activated carbon cloth (ACC), and quantify initial and final pH of solution after adding the ACC sample. We also leverage inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography (IC) to quantify the final background concentrations of individual ionic species. Our results show a very good agreement between experiments and model. The model is extendable to a wide variety of porous electrode systems and CDI systems with applied potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

The Drosophila DOCK family protein Sponge is required for development of the air sac primordium

Dedicator of cytokinesis (DOCK) family genes are known as DOCK1-DOCK11 in mammals. DOCK family proteins mainly regulate actin filament polymerization and/or depolymerization and are GEF proteins, which contribute to cellular signaling events by activating small G proteins. Sponge (Spg) is a Drosophila counterpart to mammalian DOCK3/DOCK4, and plays a role in embryonic central nervous system development, R7 photoreceptor cell differentiation, and adult thorax development. In order to conduct further functional analyses on Spg in vivo, we examined its localization in third instar larval wing imaginal discs. Immunostaining with purified anti-Spg IgG revealed that Spg mainly localized in the air sac primordium (ASP) in wing imaginal discs. Spg is therefore predicted to play an important role in the ASP. The specific knockdown of Spg by the breathless-GAL4 driver in tracheal cells induced lethality accompanied with a defect in ASP development and the induction of apoptosis. The monitoring of ERK signaling activity in wing imaginal discs by immunostaining with anti-diphospho-ERK IgG revealed reductions in the ERK signal cascade in Spg knockdown clones. Furthermore, the overexpression of D-raf suppressed defects in survival and the proliferation of cells in the ASP induced by the knockdown of Spg. Collectively, these results indicate that Spg plays a critical role in ASP development and tracheal cell viability that is mediated by the ERK signaling pathway. - Highlights: • Spg mainly localizes in the air sac primordium in wing imaginal discs. • Spg plays a critical role in air sac primordium development. • Spg positively regulates the ERK signal cascade.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Climate and edaphic controllers influence rhizosphere community assembly for a wild annual grass

The interface between roots and soil, known as the rhizosphere, is a dynamic habitat in the soil ecosystem. Unraveling the factors that control rhizosphere community assembly is a key starting point for understanding the diversity of plant-microbial interactions that occur in soil. The goals of this study were to determine how environmental factors shape rhizosphere microbial communities, such as local soil characteristics and the regional climate, and to determine the relative influence of the rhizosphere on microbial community assembly compared to the pressures imposed by the local and regional environment. We identified the bacteria present in the soil immediately adjacent to the roots of wild oat (Avena spp.) in three California grasslands using deep Illumina 16S sequencing. Rhizosphere communities were more similar to each other than to the surrounding soil communities from which they were derived, despite the fact that the grasslands studied were separated by hundreds of kilometers. The rhizosphere was the dominant factor structuring bacterial community composition (38% variance explained), and was comparable in magnitude to the combined local and regional effects (22% and 21%, respectively). Rhizosphere communities were most influenced by factors related to the regional climate (soil moisture and temperature), while background soil communities were more influenced by soil characteristics (pH, CEC, exchangeable cations, clay content). The Avena core microbiome was strongly phylogenetically clustered according to the metrics NRI and NTI, which indicates that selective processes likely shaped these communities. Furthermore, 17% of these taxa were not detectable in the background soil, even with a robust sequencing depth of approximately 70,000 sequences per sample. In conclusion, these results support the hypothesis that roots select less abundant or possibly rare populations in the soil microbial community, which appear to be lineages of bacteria that have made a physiological tradeoff for rhizosphere competence at the expense of their competitiveness in non-rhizosphere soil.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Review and Summary of Oxide Thickness Data for Aluminum-Clad Spent Nuclear Fuel

The U.S. Department of Energy (DOE) owns a large inventory of aluminum-clad spent nuclear fuel (ASNF) in interim storage pending ultimate disposition, with more being generated by currently operating research reactors. Dry storage in sealed DOE Standard Canisters is being investigated as an approach for long-term interim storage and/or disposition in a repository for ASNF. A primary challenge for ASNF storage is the presence of aluminum (oxy)hydroxide layers formed on the cladding surfaces during water exposure in the reactor and in wet storage, which forms a reservoir of chemisorbed water not readily removed at low (<100°C) drying temperatures. Free, physisorbed, and chemisorbed water are all susceptible to radiolytic breakdown under irradiation and can release hydrogen gas. Identifying the likely range of (oxy)hydroxide loadings on ASNF that may be placed in dry storage will help to ensure that the impact of the (oxy)hydroxide is adequately accounted for while avoiding over conservatism and enable mitigation strategies to be implemented where needed. The current report summarizes information on (oxy)hydroxide thicknesses and characteristics from the literature and from recent measurements taken in the present research campaign. In general, corrosion studies have indicated that the corrosion and oxide buildup on aluminum are affected by numerous conditions, including pH, temperature and heat flux, coolant flowrates, irradiation (in-reactor vs. unirradiated tests), duration of water exposure, and the amount of oxide already on the surface. Some of these factors are interrelated (e.g., the local temperature, heat flux, and coolant flowrate). Observations of the impact of irradiation (in-reactor versus ex-reactor measurements) on corrosion and oxide thickness are mixed, but multiple studies indicate that there is a significant difference between in-reactor and ex-reactor corrosion kinetics, even when other operating conditions such as pH, flowrate, heat flux, etc., simulate those in a reactor.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1961

Photosynthetic Gas Exchange in the Closed Ecosystem for Space. Phase II, Part II. Studies on the Growth of Thermophilic Chlorella 71105

Bench-scale studies with Chlorella pyrenoidosa 71105 were conducted in four- and eight-liter culture vessels, with and without recycling. It was established that the algal strain could be maintained for periods up to 72 days with supplemented re-cycled medium. In a factorial series of experiments, the highest yields were obtained with a 2.0% concentration of carbon dioxide, a 0.07 dilution factor (nutrient dilution rate/culture volume), and an 8.5 ft(exp -1) ratio of light surface to liquid culture volume. Optimum pH and concentrations of the constituents of the growth medium were determined in corollary test-tube studies. Other test-tube studies showed that the nutrient medium used for mass culture could be stored up to five weeks at 25 C or at refrigerator temperature (4 C) with little change in nitrogen-urea level. Algal suspensions stored at 4 C remained viable for periods of at least 12 weeks; growth resumed after a lag period when stored suspensions were cultured at 39 C. Streptomycin was found suitable for controlling a blue-green containment.

ALGAE↗
DOE OSTI2018

Probing Cytochrome c Folding Transitions upon Phototriggered Environmental Perturbations Using Time-Resolved X-ray Scattering

Direct tracking of protein structural dynamics during folding–unfolding processes is important for understanding the roles of hierarchic structural factors in the formation of functional proteins. As such, using cytochrome c (cyt c) as a platform, we investigated its structural dynamics during folding processes triggered by local environmental changes (i.e., pH or heme iron center oxidation/spin/ligation states) with time-resolved X-ray solution scattering measurements. Starting from partially unfolded cyt c, a sudden pH drop initiated by light excitation of a photoacid caused a structural contraction in microseconds, followed by active site restructuring and unfolding in milliseconds. In contrast, the reduction of iron in the heme via photoinduced electron transfer did not affect conformational stability at short timescales (<1 ms), despite active site coordination geometry changes. These results demonstrate how different environmental perturbations can change the nature of interaction between the active site and protein conformation, even within the same metalloprotein, which will subsequently affect the folding structural dynamics.

Rimmerman, Dolev↗
DOE OSTI2015

Monitoring of U(VI) Bioreduction after ARCADIS demonstration at Savannah River Site F-Area - 15699

The F/H Area Seepage Basins located in the center of Savannah River Site (SRS) received approximately 1.8 billion gallons of acidic waste solutions. The acidic nature of the basin waste solutions triggered the mobilization of metals and radionuclides including soluble uranium (VI). SRS F-Area sediments are acidic and composed predominantly of quartz sand with varying amounts of fine-grained minerals and iron-oxides. In 2010, ARCADIS implemented in-situ injections of a carbohydrate substrate to establish anaerobic reactive zones for metal and radionuclide remediation via the Enhanced Anaerobic Reductive Precipitation (EARP) process at the SRS F-Area (Figure 2). The addition of the molasses substrate solution to groundwater produces anaerobic conditions with redox values in the methanogenic or sulfate-reducing range conducive to the reductive precipitation of uranium. Objectives: Determine the mineral composition of SRS fine clay fractions and identify all iron-oxide phases. Establish if ferrous carbonate and ferrous sulfide compounds will be present in the sediment after the bioreduction process has occurred. The presence of these compounds will indicate that anaerobic reductive conditions were established. Determine the types of reactions that might occur in the anaerobic aquifer. Determine if conditions will return to the initial state once samples are returned to aerobic conditions. Microcosm studies were prepared with SRS sediments treated using a basal medium solution augmented with sulfate and molasses as well as a trace metal solution. To create anaerobic conditions necessary for the experiment, a vinyl anaerobic airlock chamber from COY Lab Products was used to ensure that no oxygen reached the samples. Half of the samples were augmented with sulfate in an attempt to create iron sulfide and stabilize reduced uranium. A pH evolution study was conducted to find the type of pH changes that occurred in the samples. Samples were sieved to 180 mm before X-ray Diffraction (XRD) analysis was conducted to identify any mineralogical changes in the samples. The experimental patterns were compared against known XRD patterns for siderite and pyrite. Liquid samples were filtered through 0.45 mm filters and were diluted by a factor of 200 in nitric acid (1%) for ICP-OES analysis to determine the ferrous iron concentration. XRD analysis indicated that the sediments contained quartz, kaolinite, montmorillonite, and goethite. All of the samples have followed a similar trend, with a decline in the pH values. It was noted that samples amended with sulfates had slightly higher pH than sulfate-free samples. The pH drop can be attributed to the fermentation process of molasses and the natural acidity of SRS soil used for the microcosm study. The low pH conditions are believed to have hindered the formation of bicarbonate/carbonate ions used to form the iron precipitates. XRD results confirmed the assumption that with low pH values no iron compounds would precipitate in the samples. The experimental patterns for each sample was compared with the patterns for siderite and pyrite; the results for these analyses were negative. ICP-OES analysis confirmed that there is ferrous iron present in the samples. The highest iron concentration being 13312.8 ppb for Batch 1, Sample 1-2, the lowest were in Batch 2 Samples 2,3, and 4 which may be below the calibration curve. This may also be an indication that the iron has precipitated in these samples. Future work: Conduct ICP analysis on the Batch 2 samples using a lower dilution factor. Determine the types of reactions that might occur in the anaerobic aquifer. Verify the continued sequestration of U(VI) in relation to the possible re-oxidation of minerals from the bioreduction zone. Sulfate concentrations will be examined using an ion analysis technique. Determine pH levels, sulfate concentrations, and iron concentrations after re-oxygenation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

Moment-based, self-consistent linear analysis of gyrotron oscillators

A new model for simulating gyrotron oscillators in the monomode time-dependent linear self-consistent regime is presented. Starting from a nonlinear time-dependent monomode model, the linearization and the following simplification of the model, based on a moment approach, are described. This simplified model represents a numerically efficient model and allows to have a deeper physical insight, in particular, for regimes dominated by self-consistent effects such as for the gyro-backward wave instability. One specific case of a gyrotron cavity is studied in detail and compared with experimental results, with special attention to self-consistent effects and to the differences with a model using a fixed field profile. Self-consistent linear simulations are, amongst other applications, important for the design of frequency-tunable gyrotrons or high-power gyrotrons with cavities having a relatively low quality factor, but also for studies of parasitic oscillations as they may occur in beam ducts and/or in the launcher section following the interaction cavity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Evolution of nano-rheological properties of Nafion{sup ®} thin films during pH modification by strong base treatment: A static and dynamic force spectroscopy study

Addition of a strong base to Nafion{sup ®} proton exchange membranes is a common practice in industry to increase their overall performance in fuel cells. Here, we investigate the evolution of the nano-rheological properties of Nafion thin films as a function of the casting pH, via characterization with static and dynamic, contact and intermittent-contact atomic force microscopy (AFM) techniques. The addition of KOH causes non-monotonic changes in the viscoelastic properties of the films, which behave as highly dissipative, softer materials near neutral pH values, and as harder, more elastic materials at extreme pH values. We quantify this behavior through calculation of the temporal evolution of the compliance and the glassy compliance under static AFM measurements. We complement these observations with dynamic AFM metrics, including dissipated power and virial (for intermittent-contact-mode measurements), and contact resonance frequency and quality factor (for dynamic contact-mode measurements). We explain the non-monotonic material property behavior in terms of the degree of ionic crosslinking and moisture content of the films, which vary with the addition of KOH. This work focuses on the special case study of the addition of strong bases, but the observed mechanical property changes are broadly related to water plasticizing effects and ionic crosslinking, which are also important in other types of films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Global pattern and controls of soil microbial metabolic quotient

The microbial metabolic quotient (MMQ), microbial respiration per unit of biomass, is a fundamental factor controlling heterotrophic respiration, the largest carbon flux in soils. The magnitude and controls of MMQ at regional scale remain uncertain. We compiled a comprehensive data set of MMQ to investigate the global patterns and controls of MMQ in top 30 cm soils. Published MMQ values, generally measured in laboratory microcosms, were adjusted on ambient soil temperature using long-term (30 yr) average site soil temperature and a Q10 = 2. The area-weighted global average of MMQ_Soil is estimated as 1.8 (1.5–2.2) (95% confidence interval) lmol C•h -1 •mmol -1 microbial biomass carbon (MBC) with substantial variations across biomes and between cropland and natural ecosystems. Variation was most closely associated with biological factors, followed by edaphic and meteorological parameters. MMQ_Soil was greatest in sandy clay and sandy clay loam and showed a pH maximum of 6.7 - 0.1 (mean ± se). At large scale, MMQ_Soil varied with latitude and mean annual temperature (MAT), and was negatively correlated with microbial N:P ratio, supporting growth rate theory. These trends led to large differences in MMQ_Soil between natural ecosystems and cropland. When MMQ was adjusted to 11°C (MMQ_Ref), the global MAT in the top 30 cm of soils, the area-weighted global averages of MMQ_Ref was 1.5 (1.3–1.8) lmol C•mmol MBC -1 •h -1 . The values, trends, and controls of MMQ_Soil add to our understanding of soil microbial influences on soil carbon cycling and could be used to represent microbial activity in global carbon models.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2019

Investigating Additively Manufactured 17-4 PH for Structural Applications

17-4 is used regularly to manufacture force transducers particularly for wind tunnel testing. Such applications place demanding structural requirements on the transducers with static safety factors of 1.5 common and the potential for additional dynamic loads. Additive manufacturing (AM) of transducers is very appealing because of significant potential cost and time savings as well as increased design flexibility. This study looks at the processing of 17-4 powder using selective laser melting by two different facilities using their own best practices. Hot isostatic pressing (HIP) is used by both facilities as part of the thermomechanical processing following printing to explore whether it can improve the consistency of mechanical properties. Results revealed that HIP reduced average porosity of 17-4 parts and that the yield strength of parts following solutionization and aging met wrought material property targets. Strain to failure of one of the facilities parts was less than 5% compared to greater than 9% for the other facility. Inspection of failure surfaces revealed this discrepancy could be attributed to pores (2-4% area fraction) on the failure surface of the low ductility parts. Phase content varied between the facilities with one facility producing fully martensitic parts and the other containing some retained austenite. The phase content of the starting powder and a slower than air cooling rate following the final heat treatment above the austenite eutectoid temperature are likely sources of the retained austenite. Taken together these results suggest that the current state of the art in AM 17-4 processing is sufficient for many NASA force measurement applications, but that attention is required at each stage of processing to assure desired mechanical properties.

Burns, Devin E.↗
DOE OSTI2024

Rhizosphere Soil Biogeochemical Data and Photosynthetic Data of Vicia Faba in a Rhizobox

Here we share the data in column format via csv files for pH, redox, and dissolved oxygen collected at hourly resolution from microelectrodes. Dissolved organic carbon concentrations collected from TOC are also provided in a similar format but are composited samples from hourly microdialysis collection. This provided resolution of diel rhizosphere dynamics belowground. Plant physiological data was also collected at every 5 min for 24 hr cycles in order to capture diel dynamics aboveground. This data was used to parameterize the reaction transport model eSTOMP-ROOTS, which examines the rhizosphere biogeochemistry of a growing Vicia faba plant. The aim was to investigate plant activity and belowground biogeochemical processes, particularly their impact on mineral-organic associations in the rhizosphere. We combined in-situ rhizosphere microsensor and plant physiological measurements with a 3-D plant-soil reactive transport model to explore the behavior of dissolved organic carbon (DOC) in the rhizosphere. Over several days, microdialysis probes placed at the root-soil interface in live soil showed distinct daily patterns of DOC concentration in the pore water. Spikes in DOC concentrations during the day aligned with peaks in leaf-level photosynthesis, accompanied by decreasing redox potential and dissolved oxygen levels, and increasing pH in the rhizosphere. This new mechanistic modeling framework, which integrates aboveground plant physiological data with non-destructive, high-resolution monitoring of rhizosphere processes, offers significant potential for studying the factors that control carbon storage in soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Enhanced pozzolanic reactivity in hydrogen-form zeolites as supplementary cementitious materials

Pozzolans rich in silica and alumina react with lime to form cementing compounds and are incorporated into portland cement as supplementary cementitious materials (SCMs). However, pozzolanic reactions progress slower than portland cement hydration, limiting their use in modern construction due to insufficient early-age strength. Hence, alternative SCMs that enable faster pozzolanic reactions are necessary including synthetic zeolites, which have high surface areas and compositional purity that indicate the possibility of rapid pozzolanic reactivity. Synthetic zeolites with varying cation composition (Na-zeolite, H-zeolite), SiO 2 /Al 2 O 3 ratio, and framework type were evaluated for pozzolanic reactivity via Ca(OH) 2 consumption using ion exchange and in-situ X-ray diffraction experiments. Na-zeolites exhibited limited exchange reactions with KOH and Ca(OH) 2 due to the occupancy of acid sites by Na + and hydroxyl groups. Meanwhile, H-zeolites readily adsorbed K + and Ca 2+ from a hydroxide solution by exchanging cations with H + at Brønsted acid sites or cation adsorption at vacant acid sites. By adsorbing cations, the H-zeolite reduced the pH and increased Ca 2+ solubility to promote pozzolanic reactions in a system where Ca(OH) 2 dissolution/diffusion was a rate limiting factor. High H-zeolite reactivity resulted in 0.8 g of Ca(OH) 2 consumed per 1 g of zeolites after 16 h of reaction versus 0.4 g of Ca(OH) 2 consumed per 1 g of Na-zeolite. The H-zeolite modulated the pore fluid alkalinity and created a low-density amorphous silicate phase via mechanisms analogous to two-step C-S-H nucleation experiments. Finally, controlling these reaction mechanisms is key to developing next generation pozzolanic cementitious systems with comparable hydration rates to portland cement.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electrochemical sulfate production from sulfide-containing wastewaters and integration with electrochemical nitrogen recovery

Electrochemical methods can help manage sulfide in wastewater, which poses environmental and health concerns due to its toxicity, malodor, and corrosiveness. In addition, sulfur could be recovered as fertilizer and commodity chemicals from sulfide-containing wastewaters. Wastewater characteristics vary widely among wastewaters; however, it remains unclear how these characteristics affect electrochemical sulfate production. Here, in this study, we evaluated how four characteristics of influent wastewaters (electrolyte pH, composition, sulfide concentration, and buffer strength) affect sulfide removal (sulfide removal rate, sulfide removal efficiency) and sulfate production metrics (sulfate production rate, sulfate production selectivity). We identified that electrolyte pH (3 × difference, i.e., 25.1 to 84.9 μM h –1 in average removal rate within the studied pH range) and sulfide concentration (16 × difference, i.e., 82.1 to 1347.2 μM h –1 in average removal rate) were the most influential factors for electrochemical sulfide removal. Sulfate production was most sensitive to buffer strength (6 × difference, i.e., 4.4 to 27.4 μM h –1 in average production rate) and insensitive to electrolyte composition. Together, these results provide recommendations for the design of wastewater treatment trains and the feasibility of applying electrochemical methods to varying sulfide-containing wastewaters. In addition, we investigated a simultaneous multi-nutrient (sulfur and nitrogen) process that leverages electrochemical stripping to further enhance the versatility and compatibility of electrochemical nutrient recovery.

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

Prolonged Stability of Pb-Catalyzed CO 2 Electroreduction to Methyl Formate in Acidic Methanol

Electrochemical CO 2 reduction from renewable energy is a promising route to mitigate greenhouse gas emissions from waste sources while generating value-added products. CO 2 electroreduction in methanol is particularly interesting due to the increased CO 2 solubility compared to water and the propensity to form methyl formate, a product absent in aqueous electrolysis. Here, four factors have been identified as critical to achieving prolonged high selectivity for methyl formate production on a Pb cathode in methanol: high pH near the electrode, low bulk pH, low water content, and regeneration of Pb 2+ sites. Increasing concentration of the formic acid product was observed to induce a selectivity shift towards hydrogen, which was mitigated by the in-situ conversion of the formic acid to methyl formate via an esterification reaction. Furthermore, co-electrolysis of CO 2 with dilute molecular oxygen (4% O 2 ) led to Pb catalyst repair through in-situ surface oxidation. Using CO 2 and dilute O 2 along with single-pass catholyte flow to maintain a low formic acid concentration, sustained high selectivity for methyl formate was attained at ~60% faradaic efficiency at -20 mA cm -2 for over 72 hours.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Water Oxidation and Oxygen Monitoring by Cobalt-Modified Fluorine-Doped Tin Oxide Electrodes

Electrocatalytic water oxidation occurs at fluoride-doped tin oxide (FTO) electrodes that have been surface-modified by addition of Co(II). On the basis of X-ray photoelectron spectroscopy and transmission electron microscopy measurements, the active surface site appears to be a single site or small-molecule assembly bound as Co(II), with no evidence for cobalt oxide film or cluster formation. On the basis of cyclic voltammetry measurements, surface-bound Co(II) undergoes a pH-dependent 1e(-)/1H(+) oxidation to Co(III), which is followed by pH-dependent catalytic water oxidation. O-2 reduction at FTO occurs at -0.33 V vs NHE, allowing for in situ detection of oxygen as it is formed by water oxidation on the surface. Controlled-potential electrolysis at 1.61 V vs NHE at pH 7.2 resulted in sustained water oxidation catalysis at a current density of 0.16 mA/cm(2) with 29 000 turnovers per site over an electrolysis period of 2 h. The turnover frequency for oxygen production per Co site was 4 s(-1) at an overpotential of 800 mV at pH 7.2. Initial experiments with Co(II) on a mesoporous, high-surface-area nanoFTO electrode increased the current density by a factor of similar to 5

Kent, CA↗