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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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61 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Zinc Oxide–Graphene Nanocomposite-Based Sensor for the Electrochemical Determination of Cetirizine

A nanocomposite electrode of graphene (Gr) and zinc oxide (ZnO) nanoparticles was fabricated to study the electrochemical oxidation behavior of an anti-inflammatory drug, i.e., cetirizine (CET). The voltametric response of CET for bare CPE, Gr/CPE, ZnO/CPE, and the ZnO-Gr nanocomposite electrode was studied. The modifier materials were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray powder diffraction (XRD) to comprehend the surface morphology of the utilized modifiers. The influence of pH, scan rate, and accumulation time on the electrooxidation of CET was examined. It was found that the electrochemical oxidation of CET was diffusion-controlled, in which two protons and two electrons participated. The detection limit was found to be 2.8 × 10 -8 M in a linearity range of 0.05–4.0 µM. Study of excipients was also performed, and it was found that they had negligible interference with the peak potential of CET. The validation and utility of the fabricated nanocomposite sensor material were examined by analyzing clinical and biological samples. Stability testing of the nanocomposite electrode was conducted to assess the reproducibility, determining that the developed biosensor has good stability and high efficiency in producing reproducible results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

JSC ECLSS R/T Program Overview

Viewgraphs on Johnson Space Center Environmental Control and Life Support System (ECLSS) research and technology program overview are presented. Topics covered include: advancements in electrochemical CO2 removal; supercritical water waste oxidation; electrooxidation for post-treatment of reclaimed water; and photocatalytic post-treatment of reclaimed water.

Behrend, A. F.↗
DOE OSTI2023

Enhanced Urea Oxidation Electrocatalytic Activity by Synergistic Cobalt and Nickel Mixed Oxides

In this study, exploring reactive and selective Ni-based electrocatalysts for the urea oxidation reaction (UOR) is crucial for developing urea-related energy conversion technologies. Herein, synergistic interactions in Ni/Co mixed oxides/hydroxides enhanced the UOR with low onset potential, fast reaction kinetics, and good selectivity against oxygen evolution reaction (OER). Our electrochemical measurements and theoretical calculations signified the collaborative interaction of Ni/Co mixed oxide/hydroxide heterostructures to enhance UOR activity. Our results showed that Ni 3+ species, formed at high anodic potential, produced a high anodic current primarily from unwanted OER. Instead, the Ni/Co heterostructures with dominant Ni 2+ and Co 3+ species remained stable at low anodic potential and exhibited anodic current exclusively attributed to UOR. This work highlights the importance of tuning valence charges for designing high-performance and selective UOR electrocatalysts to benefit the environmental remediation of urea runoff and enable urea electrolysis for hydrogen production by replacing conventional OER with UOR at the anode.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Electrocatalytic Oxidation of Alcohol with Cobalt Triphosphine Complexes

Coordination of the tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (P3) to cobalt forms [(CH3CN)2CoIIP3](BF4)2 (CoIIP3). In the presence of the Brönsted base iPr2EtN, CoIIP3 electrocatalytically oxidizes benzyl alcohol (BnOH) to benzaldehyde at an applied potential of -630 mV vs Fc+/0 with a TON of 19.9. In a noncatalytic reaction with excess BnOH and iPr2EtN, CoIIP3 is reduced by one electron to [(CH3CN)2CoIP3]BF4 (CoIP3) with concomitant formation of half an equivalent of benzaldehyde. This stoichiometric oxidation of BnOH suggests electron transfer occurs between intermediate cobalt species and starting CoIIP3. Kinetics and computational studies support an unfavorable alcohol binding preequilibrium step followed by favorable deprotonation of bound alcohol.

Electrocatalysis, Alcohol oxidation, Electrooxidat↗
DOE OSTI2022

Role of High-Spin Species and Pendant Amines in Electrocatalytic Alcohol Oxidation by a Nickel Phosphine Complex

We report the development of active and efficient electrocatalysts for oxidation of alcohols using earth-abundant metals will aid the progress towards a renewable energy economy. Here we present a detailed mechanistic study of electrocatalytic benzyl alcohol oxidation by a molecular nickel complex containing pendant amines using a combination of kinetic studies, NMR spectroscopy, and density functional theory. The catalyst preferentially binds alcohol in high-spin octahedral geometry, but this complex is not readily deprotonated by exogeneous base and inhibits catalysis. Dissociation of one or more solvent ligands returns the complex to a low-spin state that can be deprotonated. Kinetic modeling indicates the off-cycle high-spin intermediate lowers the catalytic turnover frequency by a factor of eight, suggesting that substantial gains in activity can be attained by improvements to the catalyst coordination geometry. In a second finding, we demonstrate the pendant amine of the catalyst only functions as a proton relay for the potential-determining step, oxidation of a nickel hydride intermediate, but does not have a substantial impact on the overall rate for oxidation of benzyl alcohol to benzaldehyde. This result contradicts the common expectation for pendant amines to participate in rate-limiting proton transfer reactions.

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

Resolving Atomic-Scale Structure and Chemical Coordination in High-Entropy Alloy Electrocatalysts for Structure–Function Relationship Elucidation

The recent breakthrough in confining five or more atomic species in nanocatalysts, referred to as high-entropy alloy nanocatalysts (HEAs), has revealed the possibilities of multielemental interactions that can surpass the limitations of binary and ternary electrocatalysts. The wide range of potential surface configurations in HEAs, however, presents a significant challenge in resolving active structural motifs, preventing the establishment of structure-function relationships for rational catalyst design and optimization. Here, we present a methodology for creating sub-5 nm HEAs using an aqueous-based peptide-directed route. Using a combination of pair distribution function and X-ray absorption spectroscopy, HEA structure models are constructed from reverse Monte Carlo modeling of experimental data sets and showcase a clear peptide-induced influence on atomic-structure and chemical miscibility. Coordination analysis of our structure models facilitated the construction of structure-function correlations applied to electrochemical methanol oxidation reactions, revealing the complex interplay between multiple metals that leads to improved catalytic properties. Our results showcase a viable strategy for elucidating structure-function relationships in HEAs, prospectively providing a pathway for future materials design.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Anodic Dissolution Rates Accelerate with Decreasing MoS 2 Nanoflake Thickness

Electrochemical gating of 2D transition metal dichalcogenide (TMD) electrodes is an emerging frontier in the field of semiconductor electrochemistry. In this approach, an applied bias modifies the charge carrier concentration of the 2D TMD, causing band edge shifts and drastic changes in charge transfer rates. However, leveraging this effect for (photo)electrocatalysis is practically limited by the stability of the TMD material under gating conditions. Gerischer showed anodic dissolution of bulk TMD electrodes can occur in the dark and hypothesized that the reaction proceeds via an electron tunneling mechanism from surface states to the TMD conduction band [H. Gerischer, D. Ross, and M. Lubke, Z. Physickalische Chem., 139, 1 (1984)]. Here we investigate this possibility in single MoS 2 nanoflakes using in situ optical microscopy and explore whether Gerischer’s electron tunneling mechanism can explain anodic dissolution rates of thin 2D semiconductors. Here, spatially resolved measurements show anodic dissolution initiates at perimeter edge sites and accelerates exponentially with decreasing layer thickness, consistent with Gerischer’s tunneling mechanism. Interestingly, single layer MoS 2 is impervious to anodic dissolution at applied potentials >200 mV more positive than those required to drive dissolution in bulk and multilayer-thick nanoflakes.

2D semiconductor↗