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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

In situ monitoring of lanthanide reactions with oxide species via combined absorption spectroscopy and electrochemical methods

Molten salts for engineering scale applications of spent nuclear fuel pyrochemical processing will inevitably have some level of oxygen impurities which can form various insoluble oxide and oxychloride species with uranium and fission products. This work demonstrates real-time concentration monitoring of two trivalent lanthanide (Ln3+) fission products, Nd3+ and Pr3+, and their reactions with oxygen (O2-) impurities to form insoluble products in LiCl-NaCl-KCl eutectic salt. A combination of high-temperature absorption spectroscopy and electrochemical testing were used to track lanthanide concentrations. O2- impurity levels were controlled in the range of 0.001 M to 0.5 M by adding Li2O to lanthanide-salt solutions. After the introduction of O2- impurities, Ln3+ concentrations were monitored via time-resolved absorption spectroscopy. Concentrations of both Ln3+ species in solution decreased with time as insoluble products formed. The initial impurity concentration controlled whether insoluble products were predominantly oxychlorides (LnOCl) or mixtures of oxychlorides and oxides (Ln2O3). However, absorption spectroscopy is limited for weakly absorbing species, such as Pr3+, and under conditions of high impurity concentrations where solutions can be turbid. To circumvent this limitation, the concentrations of Pr3+ were monitored with square wave voltammetry (SWV). Estimated reaction rates and extent of Pr3+ removal from solution as monitored by SWV agreed to within ~10% of the results found from absorption spectroscopy monitoring. This demonstrates that simultaneous electrochemical testing complements and expands the capabilities of absorption spectroscopy to monitor reactions of fission products in molten salts.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Understanding Electrical Conduction and Nanopore Formation During Controlled Breakdown

Controlled breakdown has recently emerged as a highly appealing technique to fabricate solid-state nanopores for a wide range of biosensing applications. This technique relies on applying an electric field of approximately 0.4–1 V nm –1 across the membrane to induce a current, and eventually, breakdown of the dielectric. Although previous studies have performed controlled breakdown under a range of different conditions, the mechanism of conduction and breakdown has not been fully explored. Here, electrical conduction and nanopore formation in SiN x membranes during controlled breakdown is studied. It is demonstrated that for Si-rich SiN x , oxidation reactions that occur at the membrane-electrolyte interface limit conduction across the dielectric. However, for stoichiometric Si 3 N 4 the effect of oxidation reactions becomes relatively small and conduction is predominately limited by charge transport across the dielectric. Several important implications resulting from understanding this process are provided which will aid in further developing controlled breakdown in the coming years, particularly for extending this technique to integrate nanopores with on-chip nanostructures.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Kinetics of the reaction of nitric oxide with hydrogen

The reaction of nitric oxide with hydrogen has been studied in the temperature range 2400-4500 K using a shock-tube technique. Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principal result of the study was the determination of the rate constant k1 for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k1 were obtained for each test through comparisons of measured and numerically predicted NO profiles. The data are fit closely by the expression k1 = 1.34 times 10 to the fourteenth power exp(-49 200/RT) cu cm/mole-sec. These data appear to be the first available for this rate constant.

Flower, W. L.↗
DOE OSTI2021

Revealing the etching process of water-soluble Au 25 nanoclusters at the molecular level

Etching (often considered as decomposition) is one of the key considerations in the synthesis, storage, and application of metal nanoparticles. However, the underlying chemistry of their etching process still remains elusive. Here, we use real-time electrospray ionization mass spectrometry to study the reaction dynamics and size/structure evolution of all the stable intermediates during the etching of water-soluble thiolate-protected gold nanoclusters (Au NCs), which reveal an unusual “recombination” process in the oxidative reaction environment after the initial decomposition process. Interestingly, the sizes of NC species grow larger and their ligand-to-metal ratios become higher during this recombination process, which are distinctly different from that observed in the reductive growth of Au NCs (e.g., lower ligand-to-metal ratios with increasing sizes). The etching chemistry revealed in this study provides molecular-level understandings on how metal nanoparticles transform under the oxidative reaction environment, providing efficient synthetic strategies for new NC species through the etching reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Observations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenes

Abstract. Chemical ionization mass spectrometry with the nitrate reagent ion (NO3- CIMS) was used to investigate the products of the nitrate radical (NO3) initiated oxidation of four monoterpenes in laboratory chamber experiments. α-Pinene, β-pinene, Δ-3-carene, and α-thujene were studied. The major gas-phase species produced in each system were distinctly different, showing the effect of monoterpene structure on the oxidation mechanism and further elucidating the contributions of these species to particle formation and growth. By comparing groupings of products based on the ratios of elements in the general formula CwHxNyOz, the relative importance of specific mechanistic pathways (fragmentation, termination, and radical rearrangement) can be assessed for each system. Additionally, the measured time series of the highly oxidized reaction products provide insights into the ratio of relative production and loss rates of the high-molecular-weight products of the Δ-3-carene system. The measured effective O:C ratios of reaction products were anticorrelated with new particle formation intensity and number concentration for each system; however, the monomer : dimer ratios of products had a small positive trend. Gas-phase yields of oxidation products measured by NO3- CIMS correlated with particle number concentrations for each monoterpene system, with the exception of α-thujene, which produced a considerable amount of low-volatility products but no particles. Species-resolved wall loss was measured with NO3- CIMS and found to be highly variable among oxidized reaction products in our stainless steel chamber.

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

Insights into the mechanism of electrochemical chloride oxidation in ethanol from X-ray photoelectron spectroscopy, quiescent solution voltammetry, and rotating ring-disk electrodes

The wide availability of bio-derived alcohols provides the impetus to develop processes that convert them to valuable chemicals. The chloride ion is a redox mediator for electrocatalytic ethanol oxidation to 1,1-diethoxyethane (1,1-DEE) through an ethyl hypochlorite (EtOCl) intermediate, and this paper describes the chloride oxidation reaction (COR) to EtOCl on a glassy carbon (GC) electrode. Voltammetry measurements on a GC electrode in inert acetonitrile solvent combined with ex situ X-ray photoelectron spectroscopy (XPS) establish a Volmer step, where chloride ion from solution chemisorbs and is oxidized. In reactive ethanol solvent, ethanol adsorbs, and analyzing the current response in an LSV experiment supports a two-electron-transfer to form EtOCl, with chemisorption of the regenerated chloride. Koutecký–Levich (K–L) analysis on a rotating ring disk electrode (RRDE) shows that the kinetic rate constant of the COR in ethanol is on the order of 10 −8 cm s −1 , which is five orders of magnitude faster than the direct alcohol oxidation reaction in a kinetically limited regime. This hydrodynamic approach in understanding the electrochemistry of this non-aqueous system extends the possibilities for mediated electrocatalysis in neat alcohol solvents.

Van Daele, Ryan D. [University of Michigan, Ann Ar↗
NASA NTRS2012

Adaptation of Organisms by Resonance of RNA Transcription with the Cellular Redox Cycle

Sequence variation in organisms differs across the genome and the majority of mutations are caused by oxidation, yet its origin is not fully understood. It has also been shown that the reduction-oxidation reaction cycle is the fundamental biochemical cycle that coordinates the timing of all biochemical processes in that cell, including energy production, DNA replication, and RNA transcription. It is shown that the temporal resonance of transcriptome biosynthesis with the oscillating binary state of the reduction-oxidation reaction cycle serves as a basis for non-random sequence variation at specific genome-wide coordinates that change faster than by accumulation of chance mutations. This work demonstrates evidence for a universal, persistent and iterative feedback mechanism between the environment and heredity, whereby acquired variation between cell divisions can outweigh inherited variation.

Stolc, Viktor↗
DOE OSTI2022

Spectroscopic signatures and oxidation characteristics of nanosecond laser-induced cerium plasmas

Improving technologies related to the wide area environmental sampling of nuclear materials supports the nuclear nonproliferation mission of preventing the proliferation of nuclear weapons by monitoring nuclear weapons tests and detecting undeclared nuclear fuel cycle activities. Standoff, laser-based detection techniques such as laser-induced breakdown spectroscopy have the potential to offer robust, field-deployable methods that provide rapid element-specific and phase identifiable measurements over a wide range of materials. This work aims to elucidate the effects of atmospheric conditions and oxidation reactions on the highly complex and transient spectroscopic signatures of laser-induced plutonium surrogate plasmas. Time-resolved spectra of nanosecond laser ablation cerium plasmas were measured using laser-induced breakdown spectroscopy in a range of atmospheres containing low to high concentrations of oxygen. Here, the growth of strong CeO molecular emission bands was observed in the visible spectrum, where it was shown that the persistence of CeO is reduced from around 60 μs to 50 μs in oxygen rich atmospheric environments. To further investigate the growth and depletion of CeO in the laser-produced plasma, ratios of CeO-to-Ce emission were generated using integrated intensities corresponding to the Q-branch of the CeO D 1 -X 1 transitions and numerous strong atomic Ce peaks. It was determined that the fastest rate of formation of CeO in argon occurred for moderate oxygen mass fractions between 0.10 and 0.15 while the ratios were reduced at higher oxygen mass fractions (i.e., Y O 2 = 0.20) due to competing oxidation reactions and lower plasma temperatures.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Effect of Ammonia on the Electrocatalysis of Oxygen Reduction Reaction in Base

We investigated the effect of ammonia on the activity of seven benchmark oxygen reduction reaction (ORR) electrocatalysts, Pt/C, Pd/C, Au/C, Ag/C, commercial Fe–N–C, zeolitic imidazolate framework (ZIF)-based Fe–N–C (Fe-ZIF), and ZIF-based Fe,Co–N–C (Fe,Co-ZIF) in alkaline media and direct ammonia fuel cell (DAFC) relevant conditions using a rotating disk electrode. We found that ammonia exposure causes considerable ORR activity loss for all studied electrocatalysts. Should we rank the electrocatalysts in terms of their ORR activity loss and their irreversible ORR activity loss as the result of exposure to ammonia (from the highest loss to the lowest loss), we get Au/C > Pt/C ≈ Pd/C > Ag/C » commercial Fe–N–C > Fe-ZIF ≈ Fe,Co-ZIF and Pd/C > Au/C > Ag/C > commercial Fe–N–C > Fe-ZIF ≈ Fe,Co-ZIF > Pt/C, respectively. The ammonia oxidation reaction activity and adsorptive properties of the Gerisher-Mauerer reaction intermediates do not govern the trend of the ORR activity loss of Pt/C, Pd/C, Au/C, and Ag/C electrocatalysts. Notably, we found that Pt/C electrocatalyst shows the lowest irreversible ORR activity loss, while Fe-ZIF and Fe,Co-ZIF electrocatalysts show the lowest overall ORR activity loss. Our comprehensive study suggests that Pt-based, Fe-ZIF, and Fe,Co-ZIF electrocatalysts are promising cathode candidates for future DAFCs.

Abbasi, Reza (ORCID:0000000249384151)↗
DOE OSTI2022

A single-Pt-atom-on-Ru-nanoparticle electrocatalyst for CO-resilient methanol oxidation

Single Pt atom catalysts are key targets because a high exposure of Pt substantially enhances electrocatalytic activity. In addition, PtRu alloy nanoparticles are the most active catalysts for the methanol oxidation reaction. To combine the exceptional activity of single Pt atom catalysts with an active Ru support we must overcome the synthetic challenge of forming single Pt atoms on noble metal nanoparticles. In this report we demonstrate a process that grows and spreads Pt islands on Ru branched nanoparticles to create single-Pt-atom-on-Ru catalysts. By following the spreading process by in situ TEM, we found that the formation of a stable single atom structure is thermodynamically driven by the formation of strong Pt–Ru bonds and the lowering of the surface energy of the Pt islands. The stability of the single-Pt-atom-on-Ru structure and its resilience to CO poisoning result in a high current density and mass activity for the methanol oxidation reaction over time.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Concentration-response gene expression analysis in zebrafish reveals phenotypically-anchored transcriptional responses to retene

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants and are associated with human disease. Canonically, many PAHs induce toxicity via activation of the aryl hydrocarbon receptor (AHR) pathway. While the interaction between PAHs and the AHR is well-established, understanding which AHR-regulated transcriptional effects directly result in observable phenotypes and which are adaptive or benign is important to better understand PAH toxicity. Retene is a frequently detected PAH in environmental sampling and has been associated with AHR2-dependent developmental toxicity in zebrafish, though its mechanism of toxicity has not been fully elucidated. To interrogate transcriptional changes causally associated with retene toxicity, we conducted whole-animal RNA sequencing at 48 hours post-fertilization after exposure to eight retene concentrations. The concentrations were selected to produce effects ranging from no phenotype to mortality and malformations in 100% of animals at 5 days post-fertilization. We identified a concentration-response relationship between retene teratogenicity and differential gene expression in both number of DEGs and magnitude of expression change. Elevated expression of cyp1a at retene concentrations below the threshold for teratogenicity suggested that while cyp1a expression is a sensitive biomarker of AHR activation, it may be too sensitive to serve as a biomarker of AHR-dependent teratogenicity. Genes differentially expressed at only non-teratogenic concentrations were enriched for transforming growth factor-ß (TGF-ß) signaling pathway disruption while DEGs identified at only teratogenic concentrations were significantly enriched for response to xenobiotic stimulus and reduction-oxidation reaction activity. DEGs which spanned both non-teratogenic and teratogenic concentrations showed similar disrupted biological processes to those unique to teratogenic concentrations, indicating these processes were disrupted at low exposure concentrations. Gene co-expression network analysis identified several gene modules, including those associated with PAHs and AHR2 activation. One, Module 7, was strongly enriched for AHR2-associated genes and contained the strongest responses to retene. Benchmark concentration (BMC) of Module 7 genes identified a median BMC of 7.5 µM, nearly the highest retene concentration with no associated teratogenicity, supporting the hypothesis that Module 7 genes are largely responsible for retene toxicity.

Toxin, Zebrafish, Retene, Transcriptomics, network↗
DOE OSTI2020

Laser-induced digital oxidation for copper-based flexible photodetectors

Copper oxide compounds (Cu x O) with bandgaps of 1.3–2.1 eV (CuO) and 2.1–2.6 eV (Cu 2 O) have been investigated as promising p-type semiconducting materials. Cu x O is generally obtained by deposition or thermal oxidation, but those methods are not optimal for flexible substrates. Furthermore, additional patterning steps are required to fabricate devices. In this work, we present an easy, controllable method to fabricate a metal-semiconductor-metal (MSM) photodetector using laser-induced oxidation of a thin Cu film. After laser irradiation, the Cu film is heated under ambient conditions, and this leads to a thermal oxidation reaction, in which Cu oxide is monolithically formed in the Cu film and a Cu-Cu x O-Cu MSM structure is produced. Since the laser offers localized heating, an arbitrary CuxO pattern can be written in the Cu film by spatially controlled heating. In addition, by optimizing the heating time, the laser-induced oxidation can be successfully performed even on a flexible substrate. To study the laser-induced oxidation, we examined the correlation between laser parameters and the oxidation pattern and analyzed the composition using scanning electron microscopy, Raman spectroscopy, and X-ray photoemission spectroscopy. Furthermore, we measured the transient photoresponse and employed scanning photocurrent microscopy to investigate the mechanism of carrier transport behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Theoretical Calculation Guided Design of Single-Atom Catalysts toward Fast Kinetic and Long-Life Li–S Batteries

Lithium–sulfur (Li–S) batteries are enticing next-generation energy storage technologies due to their high theoretical energy density, environmental friendliness, and low cost. Yet, low conductivity of sulfur species, dissolution of polysulfides, poor conversion from sulfur reduction, and lithium sulfide (Li 2 S) oxidation reactions during discharge–charge processes hinder their practical applications. Herein, under the guidance of density functional theory calculations, we have successfully synthesized large-scale single atom vanadium catalysts seeded on graphene to achieve high sulfur content (80 wt % sulfur), fast kinetic (a capacity of 645 mAh g –1 at 3 C rate), and long-life Li–S batteries. Both forward (sulfur reduction) and reverse reactions (Li 2 S oxidation) are significantly improved by the single atom catalysts. This finding is confirmed by experimental results and consistent with theoretical calculations. The ability of single metal atoms to effectively trap the dissolved lithium polysulfides (LiPSs) and catalytically convert the LiPSs/Li 2 S during cycling significantly improved sulfur utilization, rate capability, and cycling life. Our work demonstrates an efficient design pathway for single atom catalysts and offers solutions for the development of high energy/power density Li–S batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Red Light-Powered Nanowire Photochemical Diodes for Unassisted Hydrogen Evolution and Glycerol Valorization

Artificial photosynthesis via unassisted photochemical diodes is a promising approach for generating solar fuels. However, photoelectrochemical systems often degrade under solar diurnal cycling, and reliance on solar insolation exacerbates land use. Narrow-band LED illumination offers continuous and constant operation, enabling the vertical integration of stable photochemical diodes. In this study, 740 nm red light was investigated as the illumination source for silicon-based photochemical diodes integrating the hydrogen evolution reaction with the glycerol oxidation reaction (GOR), where replacing the oxygen evolution reaction with GOR increases attainable bias-free photocurrents. Increasing photovoltages, saturation current densities, and power conversion efficiencies were observed with increasing incident red light intensity. Under a red light intensity of 60 mW cm –2 , these systems are stable above 7.5 mA cm –2 for 6 days with periodic electrolyte refreshing. In conclusion, these results offer a promising prospect for red light-powered photochemical diodes that integrate other significant reduction reactions, such as CO 2 reduction.

Alcohols↗
DOE OSTI2024

Unlocking the potential: machine learning applications in electrocatalyst design for electrochemical hydrogen energy transformation

Machine learning (ML) is rapidly emerging as a pivotal tool in the hydrogen energy industry for the creation and optimization of electrocatalysts, which enhance key electrochemical reactions like the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), the hydrogen oxidation reaction (HOR), and the oxygen reduction reaction (ORR). This comprehensive review demonstrates how cutting-edge ML techniques are being leveraged in electrocatalyst design to overcome the time-consuming limitations of traditional approaches. ML methods, using experimental data from high-throughput experiments and computational data from simulations such as density functional theory (DFT), readily identify complex correlations between electrocatalyst performance and key material descriptors. Leveraging its unparalleled speed and accuracy, ML has facilitated the discovery of novel candidates and the improvement of known products through its pattern recognition capabilities. This review aims to provide a tailored breakdown of ML applications in a format that is readily accessible to materials scientists. Hence, we comprehensively organize ML-driven research by commonly studied material types for different electrochemical reactions to illustrate how ML adeptly navigates the complex landscape of descriptors for these scenarios. We further highlight ML's critical role in the future discovery and development of electrocatalysts for hydrogen energy transformation. Potential challenges and gaps to fill within this focused domain are also discussed. As a practical guide, we hope this work will bridge the gap between communities and encourage novel paradigms in electrocatalysis research, aiming for more effective and sustainable energy solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Experimental Studies of Graphene-Coated Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

The two main technical limitations of direct methanol fuel cells (DMFCs) are the slow kinetic reactions of the methanol oxidation reaction (MOR) in the anode and the crossing over of unreacted methanol through the proton exchange membrane (PEM). It is a common practice to use Nafion membranes as PEMs, which have high ion exchange capacity. However, Nafion-based membranes also have high fuel permeability, decreasing fuel utilization, and reducing the potential power density. This article focuses on using graphene-coated (Gr-coated) PEMs to reduce fuel crossover. Protons can permeate across graphene, and thus, it can be employed in various devices as a proton conductive membrane. Here, we report the efficiency of Gr-coated Nafions. We tested performance and crossover at three different temperatures with four different fuel concentrations and compared it to a Nafion PEM that underwent the same test conditions. We found that the adhesion of Gr on to PEMs is insufficient for prolonging fuel cell operation, resulting in Gr delamination at high temperatures and higher fuel crossover values compared to lower temperature testing. Furthermore, the results for 7.5M methanol fuel show a reduction of up to 25% in methanol crossover, translating to a peak power density that increases from 3.9 to 9.5 mW/cm 2 when using a Gr-coated PEM compared to a Nafion PEM at 30 °C.

25 ENERGY STORAGE↗
NASA NTRS1973

A stochastic model of turbulent mixing with chemical reaction: Nitric oxide formulation in a plug-flow burner

A stochastic model of turbulent mixing was developed for a reactor in which mixing is represented by n-body fluid particle interactions. The model was used to justify the assumption (made in previous investigations of the role of turbulent mixing on burner generated thermal nitric oxide and carbon monoxide emissions) that for a simple plug flow reactor, composition nonuniformities can be described by a Gaussian distribution function in the local fuel:air equivalence ratio. Recent extensions of this stochastic model to include the combined effects of turbulent mixing and secondary air entrainment on thermal generation of nitric oxide in gas turbine combustors are discussed. Finally, rate limited upper and lower bounds of the nitric oxide produced by thermal fixation of molecular nitrogen and oxidation of organically bound fuel nitrogen are estimated on the basis of the stochastic model for a plug flow burner; these are compared with experimental measurements obtained using a laboratory burner operated over a wide range of test conditions; good agreement is obtained.

Flagan, R. C.↗