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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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60 records · Page 4

Insensitivity of Magnetic Coupling to Ligand Substitution in a Series of Tetraoxolene Radical-Bridged Fe 2 Complexes

The elucidation of magnetostructural correlations between bridging ligand substitution and strength of magnetic coupling is essential to the development of high-temperature molecule-based magnetic materials. Toward this end, we report the series of tetraoxolene-bridged Fe II 2 complexes [(Me 3 TPyA) 2 Fe 2 ( R L)] n + (Me 3 TPyA = tris(6-methyl-2-pyridylmethyl)amine; n = 2: OMe LH 2 = 3,6-dimethoxy-2,5-dihydroxo-1,4-benzoquinone, Cl LH 2 = 3,6-dichloro-2,5-dihydroxo-1,4-benzoquinone, Na 2 [ NO 2 L] = sodium 3,6-dinitro-2,5-dihydroxo-1,4-benzoquinone; n = 4: SMe 2 L = 3,6-bis(dimethylsulfonium)-2,5-dihydroxo-1,4-benzoquinone diylide) and their one-electron-reduced analogues. Furthermore, variable-temperature dc magnetic susceptibility data reveal the presence of weak ferromagnetic superexchange between Fe II centers in the oxidized species, with exchange constants of J = +1.2(2) (R = OMe, Cl) and +0.3(1) (R = NO 2 , SMe 2 ) cm –1 . In contrast, X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy establish a ligand-centered radical in the reduced complexes. Magnetic measurements for the radical-bridged species reveal the presence of strong antiferromagnetic metal–radical coupling, with J = -57(10), -60(7), -58(6), and -65(8) cm –1 for R = OMe, Cl, NO 2 , and SMe 2 , respectively. The minimal effects of substituents in the 3- and 6-positions of R L x –• on the magnetic coupling strength is understood through electronic structure calculations, which show negligible spin density on the substituents and associated C atoms of the ring. Finally, the radical-bridged complexes are single-molecule magnets, with relaxation barriers of U eff = 50(1), 41(1), 38(1), and 33(1) cm –1 for R = OMe, Cl, NO 2 , and SMe 2 , respectively. Taken together, these results provide the first examination of how bridging ligand substitution influences magnetic coupling in semiquinoid-bridged compounds, and they establish design criteria for the synthesis of semiquinoid-based molecules and materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alkali cation-induced cathodic corrosion in Cu electrocatalysts

The reconstruction of Cu catalysts during electrochemical reduction of CO 2 is a widely known but poorly understood phenomenon. Herein, we examine the structural evolution of Cu nanocubes under CO 2 reduction reaction and its relevant reaction conditions using identical location transmission electron microscopy, cyclic voltammetry, in situ X-ray absorption fine structure spectroscopy and ab initio molecular dynamics simulation. Our results suggest that Cu catalysts reconstruct via a hitherto unexplored yet critical pathway - alkali cation-induced cathodic corrosion, when the electrode potential is more negative than an onset value (e.g., –0.4 V RHE when using 0.1 M KHCO 3 ). Having alkali cations in the electrolyte is critical for such a process. Consequently, Cu catalysts will inevitably undergo surface reconstructions during a typical process of CO 2 reduction reaction, resulting in dynamic catalyst morphologies. While having these reconstructions does not necessarily preclude stable electrocatalytic reactions, they will indeed prohibit long-term selectivity and activity enhancement by controlling the morphology of Cu pre-catalysts. Alternatively, by operating Cu catalysts at less negative potentials in the CO electrochemical reduction, we show that Cu nanocubes can provide a much more stable selectivity advantage over spherical Cu nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

A chemical analysis of soil-water mixtures and the first microscopic images of martian soil will be among the results to be returned by the Mars Environmental Compatibility Assessment (MECA) payload on the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's primary goal is to evaluate potential geochemical and environmental hazards that may confront future martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. As a survey of soil properties, the MECA data set will also be rich in information relevant to basic geology, paleoclimate, and exobiology. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. MECA is allocated a mass of 10 kg and a peak power usage of 15 W within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases. Cyclic voltammetry will address oxidants, and anodic stripping voltammetry will probe potentially hazardous trace metals. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in a controlled illumination environment to image dust and soil particles from millimeters to nanometers in size. Careful selection of substrates and an abrasion tool allows experimental study of size distribution, adhesion, abrasion, hardness, color, shape, aggregation, magnetic and other properties. Mounted on the end of the robot arm, MECA's electrometer consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultra-violet- light-induced ions and a low-voltage break-down threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. In addition, the electrostatic environment is key to transport of dust and, consequently, martian meteorology. MECA will also observe natural dust accumulation on engineering materials. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the inter-action between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. Dust accumulation as a function of conductivity, magnetic field strength, and other parameters will be explored. The MECA instruments described above will assess potential hazards that the Martian soil might present to human explorers and their equipment. In addition, MECA will provide information on the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation. Additional information is contained in the original extended abstract.

Hecht, M. H.↗

Boron‐Doped Nano‐Crystalline Coated Carbon Fibers for Phasic Dopamine Sensing

Real time, chronic electrochemical detection of neurotransmitters will provide a positive step in the treatment and understanding of neurological disease. However, current electrodes using carbon fibers (CF) fail to perform chronically. While diamond-based coatings show promise in improving their longevity, achieving a uniform layer of such coatings on CFs is challenging, and the electrodes often lose sensitivity after coating. In this work, a complete and uniform boron-doped nanocrystalline material grown in a diamond reactor (B-NCD) was developed to coat CF microelectrodes for neurochemical sensing. The coating was characterized electrically, optically, mechanically, and chemically. The B-NCD coated CF electrodes were able to detect phasic dopamine at a sensitivity comparable to the most widely used alternatives (uncoated and PEDOT:Nafion coated CFs). During biofouling testing, the B-NCD coated CF electrodes demonstrated better stability than uncoated CFs and comparable performance to PEDOT:Nafion coated CFs. Moreover, B-NCD exhibited no signs of degradation during consecutive FSCV applications, while uncoated and PEDOT:Nafion coated CF electrodes degraded significantly over time. Furthermore, the B-NCD coating supported the survival and development of neurons and astrocytes in vitro, exhibited excellent adhesion and durability during mechanical bending testing, and enabled successful in vivo recording of phasic dopamine release in the rat brain. Overall, B-NCD coated CFs present as an ideal candidate for chronic, flexible neural implantable electrodes for long-term neurochemical monitoring.

carbon fiber↗

Proton-Coupled Electron Transfer in a Ruthenium(II) Bipyrimidine Complex in Its Ground and Excited Electronic States

In this work, proton-coupled electron transfer (PCET) was studied for the ground and excited electronic states of a [Ru(terpy)(bpm)(OH 2 )(PF 6 ) 2 ] complex, Ru-bpm. Cyclic voltammetry measurements show that the Ru(II)-aqua moiety undergoes PCET to form a Ru(IV)-oxo moiety in the anodic region, while the bpm ligand undergoes PCET to form bpmH 2 in the cathodic region. The photophysical behavior of Ru-bpm was studied using steady-state and femtosecond transient UV–vis absorption spectroscopy, coupled with density functional theory (DFT) calculations. The lowest-lying excited state of Ru-bpm is described as a (Ru → bpm) metal-to-ligand charge-transfer (MLCT) state, while the metal-centered (MC) excited state was found computationally to be close in energy to the lowest-energy bright MLCT state (MC state was 0.16 eV above the MLCT state). The excited-state kinetics of Ru-bpm were found via transient absorption spectroscopy to be short-lived and were fit well to a biexponential function with lifetimes $τ_1$ = 4 ps and $τ_2$ = 65 ps in aqueous solution. Kinetic isotope effects of 1.75 ($τ_1$) and 1.61 ($τ_2$) were observed for both decay components, indicating that the solvent plays an important role in the excited-state dynamics of Ru-bpm. Based on the pH-dependent studies and the results from prior studies of similar Ru-complexes, we hypothesize that the 3 MLCT state forms an excited-state hydrogen-bond adduct with the solvent molecules and that this process occurs with a 4 ps lifetime. The formation of such a hydrogen-bond complex is consistent with the electronic density accumulation at the peripheral N atoms of the bpm moiety in the 3 MLCT state. The hydrogen-bonded state 3 MLCT decays to the ground state with a 65 ps lifetime. Such a short lifetime is likely associated with the efficient vibrational energy transfer from the 3 MLCT state to the solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's goal is to evaluate potential geochemical and environmental hazards that may confront future Martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. The instrument will acquire soil samples with a robotic arm equipped with a camera. MECA will examine surface and subsurface soil and dust in order to characterize particle size, shape, hardness, and also physical characteristics that may provide clues to mineralogy. MECA will characterize soil/water mixtures with respect to pH, redox potential, total dissolved ions, and trace toxins. MECA will determine the nature of electrostatic charging associated with excavation of soil, and the influence of ionizing radiation on material properties. It will also observe natural dust accumulation on engineering materials. To accomplish these objectives, MECA is allocated a mass of 10 kg within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential. Experiments will include cyclic voltammetry and anodic stripping voltammetry. Complementary to the Viking experiments, the chemical laboratory will characterize the water-soil solution rather than emitted gases. Nonetheless, through analysis of dissolved gases it will be able to replicate many of the Viking observations related to oxidants. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. On Earth, the earliest forms of life are preserved as microfossils. The atomic-force microscope will have the required resolution to image down to the scale of terrestrial microfossils and beyond. Mounted on the end of the robot arm, MECA's electrometer actually consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultraviolet-light-induced ions and a low-voltage breakdown threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. The field meter will measure the ambient field on nearby objects while the triboelectric sensors, using identical circuitry, will measure the charge accumulated on test substances as they are dragged through the soil by the arm. The ion chamber, open to the environment, will sense both charged dust and free ions in the air. Over and above the potential threat to electronics, the electrostatic environment holds one of the keys to transport of dust and, consequently, Martian meteorology. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the interaction between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. A third array will passively collect dust from the atmosphere. In addition to objectives related to human exploration, the MECA data set will be rich in information relevant to basic geology, paleoclimate, and exobiology issues. To understand both contemporaneous and ancient processes on Mars, the mineralogy, petrology, and reactivity of Martian surface materials should be constrained. The MECA experiment will shed light on these quantities through its combination of chemistry and microscopy. MECA will be capable of measuring the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation.

Hecht, M. H.↗