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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Tafel Slope Analyses for Homogeneous Catalytic Reactions

Tafel analysis of electrocatalysts is essential in their characterization. This paper analyzes the application of Tafel-like analysis to the four-electron nonelectrochemical oxidation of water by the stoichiometric homogeneous 1-electron oxidant [Ru(bpy)3]3+ to dioxygen catalyzed by homogeneous catalysts, [Ru4O4(OH)2(H2O)4(γ-SiW10O36)2]10− (Ru4POM) and [Co4(H2O)2(PW9O34)2]10– (Co4POM). These complexes have slow electron exchange rates with electrodes due to the Frumkin effect, which precludes the use of known electrochemical methods to obtain Tafel plots at ionic strengths lower than 0.5 M. The application of an electron transfer catalyst, [Ru(bpy)3]3+/2+, increases the rates between the Ru4POM and electrode, but a traditional Tafel analysis of such a complex system is precluded due to a lack of appropriate theoretical models for 4-electron processes. Here, we develop a theoretical framework and experimental procedures for a Tafel-like analysis of Ru4POM and Co4POM, using a stoichiometric molecular oxidant [Ru(bpy)3]3+. The dependence of turnover frequency (TOF) as a function of electrochemical solution potential created by the [Ru(bpy)3]3+/[Ru(bpy)3]2+ redox couple (an analog of the Tafel plot) was obtained from kinetics data and interpreted based on the suggested reaction mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

The influence of the ionized medium on synchrotron emission in interstellar space.

The effect of the ionized gas on synchrotron emission in the interstellar medium is investigated. A detailed calculation of the synchrotron emissivity of cosmic electrons, assumed to have an isotropic pitch-angle distribution in a uniform magnetic field, is made as a function of frequency and observation angle with respect to the field. The results are presented both as a local emissivity and as an intensity, the latter obtained by neglecting free-free absorption in the interstellar medium and by assuming that the emissivity is constant along the line of sight. The comparison of these results with previous studies on the nature of the low-frequency turnover of the galactic nonthermal radio background reveals that, except if the component perpendicular to the line of sight of the interstellar magnetic field is small (less than 1 microgauss), or if the cosmic-ray electron spectrum is cut off at energies below a few hundred MeV, the suppression of synchrotron emission by the ambient electrons has in general a lesser effect than free-free absorption by these electrons, and that in some cases this suppression effect is almost entirely negligible.

Ramaty, R.↗
NASA NTRS1973

Theory of solar microwave bursts

The theory of solar microwave bursts is discussed in terms of gyrosynchrotron emission and absorption in a magnetoactive plasma and other absorption processes by the background medium. Simplified formulas for all turnover frequencies are given. Above about 2 GHz the most likely absorption processes for large bursts are free-free absorption and gyrosynchrotron self-absorption. The former process is capable of producing flux densities which are flat or slowly varying functions of frequency. The latter process sets absolute upper limits on the intensities of microwave bursts, which at a given frequency, depend only on the magnetic field in the source region.

Ramaty, R.↗
NASA NTRS1974

Physics of compact nonthermal sources. II Determination of physical parameters

A set of restrictions upon the magnetic field and visible angular size of a canonical nonthermal source (one whose emission is incoherent electron synchrotron) has been obtained in another paper. The degree of electron anisotropy and magnetic field disordering were left as free parameters. In the present paper these restrictions are applied to the variable compact radio sources 3C 84, 3C 120, 3C 273, 3C 279, 3C 454.3, CTA 102, 3C 446, PKS 2134 + 004, VRO 42.22.01, and OJ 287. The theoretically derived angular sizes for these sources are in reasonable agreement with published VLBI sizes, provided that the characteristic pitch angles are not extremely small. The magnetic field strengths determined from the degree of circular polarization are generally compatible with field strengths derived from the self-absorption and synchrotron self-Compton conditions, again provided that the pitch angles are not too small. It is argued that the self-absorption optical depth cannot be much less than unity near the low-frequency turnovers; otherwise, serious discrepancies with observation result.

Jones, T. W.↗
NASA NTRS1979

Spectral evolution of multiply impulsive solar bursts

Some results from the analysis of a set of multiply impulsive hard X-ray and microwave solar bursts are presented, showing that some bursts can exhibit widely different magnetic-field strengths at different times. Two categories of microwave spectral behavior are identified: those events during which the microwave turnover frequency (MTF) and spectral shape (SS) remain the same from peak to peak, and those during which the MTF and SS change significantly. These categories correspond to two classes of multiply impulsive bursts: those for which the emission can be characterized by a constant magnetic field and therefore a single source region, and those in which groups of component spikes appear to originate in regions of different magnetic-field strengths, corresponding to separate source regions which flare sequentially. With regard to the latter type, examples are presented, the discrete flaring regions are examined, and their spatial separations are estimated.

Karpen, J. T.↗
NASA NTRS1986

The possible importance of synchrotron/inverse Compton losses to explain fast MM-wave and hard X-ray emission of a solar event

The solar burst of 21 May 1984 presented a number of unique features. The time profile consisted of seven major structures (seconds), with a turnover frequency or approx. 90 GHz, well correlated in time to hard X-ray emission. Each structure consisted of multiple fast pulses (.1 seconds), which were analyzed in detail. A proportionality between the repetition rate of the pulses and the burst fluxes at 90 GHz and or approx. 100 keV hard X-rays, and an inverse proportionality between repetition rates and hard X-rays power law indices have been found. A synchrotron/inverse Compton model has been applied to explain the emission of the fast burst structures, which appear to be possible for the first three or four structures.

Correia, E.↗
NASA NTRS1986

The possible importance of synchrotron/inverse Compton losses to explain fast mm-wave and hard X-ray emission of a solar event

The solar burst of 21 May 1984, presented a number of unique features. The time profile consisted of seven major structures (seconds), with a turnover frequency of greater than or approximately 90 GHz, well correlated in time to hard X-ray emission. Each structure consisted of multiple fast pulses (0.1 seconds), which were analyzed in detail. A proportionality between the repetition rate of the pulses and the burst fluxes at 90 GHz and greater than or approximately 100 keV hard X-rays, and an inverse proportionality between repetition rates and hard X-ray power law indices were found. A synchrotron/inverse Compton model was applied to explain the emission of the fast burst structures, which appear to be possible for the first three or four structures.

Correia, E.↗
NASA NTRS1986

Rapid spectral and flux time variations in a solar burst observed at various dm-mm wavelengths and at hard X-rays

A solar burst was observed with high sensitivity and time resolution at cm-mm wavelengths by two different radio observatories (Itapetinga and Algonquin), with high spectral time resolution at dm-mm wavelengths by patrol instruments (Sagamore Hill), and at hard X-rays (HXM Hinotori). At the onset of the major burst time structure there was a rapid rise in the spectral turnover frequency (from 5 to 15 GHz), in about 10s, coincident to a reduction of the spectral index in the optically thin part of the spectrum. The burst maxima were not time coincident at the optically thin radio frequencies and at the different hard X-ray energy ranges. The profiles at higher radio frequencies exhibited better time coincidence to the high energy X-rays. The hardest X-ray spectrum (-3) coincided with peak radio emission at the higher frequency (44 GHz). The event appeared to be built up by a first major injection of softer particles followed by other injections of harder particles. Ultrafast time structures were identified as superimposed on the burst emission at the cm-mm high sensitivity data at X-rays, with predominant repetition rates ranging from 2.0 to 3.5 Hz.

Zodivaz, A. M.↗
NASA NTRS1986

Far-infrared properties of optically selected quasars

The far-infrared properties of 10, optically selected quasars were studied on the basis of pointed IRAS observations and ground-based near-infrared and radio measurements. Nine of these quasars were detected in at least three IRAS bands. The flat spectral energy distributions characterizing these optically selected quasars together with large 60-100-micron luminosities suggest that the infrared emission is dominated by nonthermal radiation. Seven of the nine quasars with far-infrared detections were found to have low-frequency turnovers.

Edelson, R. A.↗
NASA NTRS1994

Millimeter, microwave, hard X-ray, and soft X-ray observations of energetic electron populations in solar flares

We present comparisons of multiwavelength data for a number of solar flares observed during the major campaign of 1991 June. The different wavelengths are diagnostics of energetic electrons in different energy ranges: soft X-rays are produced by electrons with energies typically below 10 keV, hard X-rays by electrons with energies in the range 10-200 keV, microwaves by electrons in the range 100 keV-1 MeV, and millimeter-wavelength emission by electrons with energies of 0.5 MeV and above. The flares in the 1991 June active period were remarkable in two ways: all have very high turnover frequencies in their microwave spectra, and very soft hard X-ray spectra. The sensitivity of the microwave and millimeter data permit us to study the more energetic (greater than 0.3 MeV) electrons even in small flares, where their high-energy bremsstrahlung is too weak for present detectors. The millimeter data show delays in the onset of emission with respect to the emissions associated with lower energy electrons and differences in time profiles, energy spectral indices incompatible with those implied by the hard X-ray data, and a range of variability of the peak flux in the impulsive phase when compared with the peak hard X-ray flux which is two orders of magnitude larger than the corresponding variability in the peak microwave flux. All these results suggest that the hard X-ray-emitting electrons and those at higher energies which produce millimeter emission must be regarded as separate populations. This has implications for the well-known 'number problem' found previously when comparing the numbers of non thermal electrons required to produce the hard X-ray and radio emissions.

Kundu, M. R.↗
DOE OSTI2024

Catalytic Resonance Theory: Turnover Efficiency and the Resonance Frequency

Programmable catalysts exhibiting forced oscillation in the free energy of reacting surface species were simulated to understand the general mechanisms leading to efficient use of the input energy. Catalytic ratchets with either positive or negative adsorbate scaling exhibited oscillation conditions of both high and low turnover efficiency, yielding catalytic turnover frequencies either close to or significantly lower than the applied catalyst oscillation frequency, respectively. The “effective rate”, defined as the product of the catalytic turnover frequency and the turnover efficiency (ηTOE), was limited via two catalytic mechanisms: a leaky catalytic ratchet existed when molecules repeatedly traversed backward through the catalytic transition state upon catalyst oscillation, while a catalytic ratchet with low surface participation exhibited reduced formation of a gas-phase final product due to low surface product coverage. Furthermore, a single applied frequency yielding a maximum effective catalytic rate defined as the “resonance frequency” provided maximum combined benefit for catalytic rate and efficiency.

25 ENERGY STORAGE↗
NASA NTRS1989

The radiative signature of the shock acceleration process in active galactic nuclei

A time-dependent model in which plasma enters a shock region and undergoes first-order Fermi acceleration is considered. The time evolution of the particle distribution and the associated synchrotron emission has been calculated for an energy-dependent diffusion coefficient. When the emitting region is not spatially resolved, the spectrum is a power law with an exponential turnover in frequency. With increasing time, the power law and the turnover extend to higher frequencies. To test the model, observations at three or more frequencies should be made of time-resolved flux increases from the optically thin nonthermal emission region in variable active galactic nuclei. Existing data that can be used to test the model are scarce but offer qualitative support.

Bregman, Joel N.↗
NASA NTRS1993

The spectrum and variability of radio emission from AE Aquarii

The first detections of the magnetic cataclysmic variable AE Aquarii at millimeter wavelengths are reported. AE Aqr was detected at wavelengths of 3.4 and 1.25 mm. These data are used to show that the time-averaged spectrum is generally well fitted by a power law S(nu) varies as nu exp alpha, where alpha is approximately equal to 0.35-0.60, and that the power law extends to millimeter wavelengths, i.e., the spectral turnover is at a frequency higher than 240 GHz. It is suggested that the spectrum is consistent with that expected from a superposition of flarelike events where the frequency distribution of the initial flux density is a power law f (S0) varies as S0 exp -epsilon, with index epsilon approximately equal to 1.8. Within the context of this model, the high turnover frequency of the radio spectrum implies magnetic field strengths in excess of 250 G in the source.

Abada-Simon, Meil↗
DOE OSTI2022

Effects of the method of active site characterization for determining structure-sensitivity in Ag-catalyzed ethylene epoxidation

We report catalysts have been prepared on a low surface area α-Al 2 O 3 support used commercially for previous generation olefin epoxidation catalysts. Prescreening of the low surface area alumina (0.73 m 2 /g) indicated the absence of acid catalyzed isomerization of EO at an evaluation temperature of 210 °C. A 0.1 wt% Ag base material synthesized by incipient wetness impregnation of AgNO 3 was used as a base material for electroless deposition (ED) of additional Ag to increase particle sizes by controlled reduction of Ag + directly onto the preexisting Ag surface to form weight loadings between 0.3 and 5.0 wt% metal. A 12 wt% Ag/α-Al 2 O 3 using Ag 2 C 2 O 4 as the Ag precursor was also prepared to compare performance of the ED samples with a catalyst more typical of industrial formulations. Characterization by SEM, STEM, and hydrogen titration of oxygen precovered Ag characterized before and after catalytic evaluation indicated that microscopy is required to accurately represent distributions of Ag particle sizes, but H 2 titration of O-precovered Ag gives the best representation of active sites since it directly counts the number of Ag surface sites. Larger particles >100 nm are resistant to both Ag sintering and carbon foulant; TOF values were relatively insensitive to particle size with only a 2.2 × difference between the best and worst performing samples. Selectivity, which is not a function of TOF, shows the most significant structure sensitivity effect where particle sizes follow the trend 67 nm ≈ 92 nm (58% EO) < 157 nm (67% EO) < 211–542 nm (73% EO). The lower EO selectivities were also correlated with increased fouling for the smaller Ag sizes, suggesting that more strongly bound EO precursor(s) leads to combustion and CO 2 /H 2 O formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2021

Astrophysics Milestones for Pulsar Timing Array Gravitational-wave Detection

The NANOGrav Collaboration reported strong Bayesian evidence for a common-spectrum stochastic process in its12.5 yr pulsar timing array data set, with median characteristic strain amplitude at periods of a year of A(yr) = 1.92(+0.75,-0.55) x 10^(-15). However, evidence for the quadrupolar Hellings & Downs interpulsar correlations, which are characteristic of gravitational-wave signals, was not yet significant. We emulate and extend the NANOGrav data set, injecting a wide range of stochastic gravitational-wave background(GWB)signals that encompass a variety of amplitudes and spectral shapes, and quantify three key milestones.(I)Given the amplitude measured in the 12.5 yr analysis and assuming this signal is a GWB, we expect to accumulate robust evidence of an interpulsar-correlated GWB signal with 15–17 yr of data, i.e., an additional 2–5 yr from the 12.5 yr data set.(II)At the initial detection, we expect a fractional uncertainty of 40% on the power-law strain spectrum slope, which is sufficient to distinguish a GWB of supermassive black hole binary origin from some models predicting more exotic origins.(III)Similarly, the measured GWB amplitude will have an uncertainty of 44% upon initial detection, allowing us to arbitrate between some population models of supermassive black hole binaries. In addition, power-law models are distinguishable from those having low-frequency spectral turnovers once 20 yr of data are reached. Even though our study is based on the NANOGrav data, we also derive relations that allow for a generalization to other pulsar timing array data sets. Most notably, by combining the data of individual arrays into the International Pulsar Timing Array, all of these milestones can be reached significantly earlier.

Nihan S. Pol↗
NASA NTRS1984

The scattering of energetic particles by waves in a finite beta plasma

Solutions are presented for the dispersion relation of waves propagating parallel to the ambient magnetic field, in a plasma having an arbitrary ratio of thermal to magnetic pressure, beta. Previous results applicable only to wave frequencies much lower than the ion cyclotron frequency are extended to include all frequencies lower than the electron cyclotron frequency. The cyclotron turnovers are found to occur at significantly lower frequencies in finite beta plasmas. Cyclotron damping is significant for small wavelength waves. These results show that in energetic particle scattering by electromagnetic turbulence in a plasma with beta value greater than 40, scattering by waves with wave frequencies greater than the ion cyclotron frequency can be neglected. This condition is satisfied in many astrophysical plasmas.

Davila, J. M.↗
DOE OSTI2023

Supramolecular Enhancement of Electrochemical Nitrate Reduction Catalyzed by Cobalt Porphyrin Organic Cages for Ammonia Electrosynthesis in Water**

Abstract The electrochemical nitrate (NO 3 − ) reduction reaction (NO 3 RR) to ammonia (NH 3 ) represents a sustainable approach for denitrification to balance global nitrogen cycles and an alternative to traditional thermal Haber‐Bosch processes. Here, we present a supramolecular strategy for promoting NH 3 production in water from NO 3 RR by integrating two‐dimensional (2D) molecular cobalt porphyrin ( CoTPP ) units into a three‐dimensional (3D) porous organic cage architecture. The porphyrin box CoPB‐C8 enhances electrochemical active site exposure, facilitates substrate–catalyst interactions, and improves catalyst stability, leading to turnover numbers and frequencies for NH 3 production exceeding 200,000 and 56 s −1 , respectively. These values represent a 15‐fold increase in NO 3 RR activity and 200‐mV improvement in overpotential for the 3D CoPB‐C8 box structure compared to its 2D CoTPP counterpart. Synthetic tuning of peripheral alkyl substituents highlights the importance of supramolecular porosity and cavity size on electrochemical NO 3 RR activity. These findings establish the incorporation of 2D molecular units into 3D confined space microenvironments as an effective supramolecular design strategy for enhancing electrocatalysis.

An, Lun↗
DOE OSTI2023

Supramolecular Enhancement of Electrochemical Nitrate Reduction Catalyzed by Cobalt Porphyrin Organic Cages for Ammonia Electrosynthesis in Water**

Abstract The electrochemical nitrate (NO 3 − ) reduction reaction (NO 3 RR) to ammonia (NH 3 ) represents a sustainable approach for denitrification to balance global nitrogen cycles and an alternative to traditional thermal Haber‐Bosch processes. Here, we present a supramolecular strategy for promoting NH 3 production in water from NO 3 RR by integrating two‐dimensional (2D) molecular cobalt porphyrin ( CoTPP ) units into a three‐dimensional (3D) porous organic cage architecture. The porphyrin box CoPB‐C8 enhances electrochemical active site exposure, facilitates substrate–catalyst interactions, and improves catalyst stability, leading to turnover numbers and frequencies for NH 3 production exceeding 200,000 and 56 s −1 , respectively. These values represent a 15‐fold increase in NO 3 RR activity and 200‐mV improvement in overpotential for the 3D CoPB‐C8 box structure compared to its 2D CoTPP counterpart. Synthetic tuning of peripheral alkyl substituents highlights the importance of supramolecular porosity and cavity size on electrochemical NO 3 RR activity. These findings establish the incorporation of 2D molecular units into 3D confined space microenvironments as an effective supramolecular design strategy for enhancing electrocatalysis.

An, Lun↗