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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

Energetics and kinetics of the prebiotic synthesis of simple organic acids and amino acids with the FeS-H2S/FeS2 redox couple as reductant

The thermodynamics of the FeS-H2S/FeS2 redox couple and a select number of reactions critical to the synthesis of simple carboxylic acids and amino acids have been evaluated as a function of temperature. This thermodynamic evaluation shows that the reducing power of the FeS-H2S/FeS2 redox couple decreases drastically with temperature. By contrast the equilibria describing the reduction of CO2 and the formation of simple carboxylic acids and amino acids require an increasingly higher reducing power with temperature. Given these two opposite trends, the thermodynamic driving force for CO2 reduction and amino acid formation with the FeS-H2S/FeS2 redox couple as reductant diminishes with increasing temperature. An evaluation of the mechanism of CO2 reduction by the FeS-H2S/FeS2 couple suggests that the electron transfer from pyrrhotite to CO2 is hindered by a high activation energy, even though the overall reaction is thermodynamically favorable. By comparison the electron transfer from pyrrhotite to either CS2, CO, or HCOOH are far more facile. This theoretical analysis explains the results of experimental work by Keefe et al. (1995), Heinen and Lauwers (1996) and Huber and Wachtershauser (1997). The implication is that a reaction sequence involving the reduction of CO2 with the FeS-H2S/FeS2 couple as reductant is unlikely to initiate a proposed prebiotic carbon fixation cycle (Wachtershauser, 1988b; 1990b, 1990a, 1992, 1993).

Non-NASA Center↗
NASA NTRS2013

U.S. Naval Observatory VLBI Analysis Center

This report summarizes the activities of the VLBI Analysis Center at the United States Naval Observatory for the 2012 calendar year. Over the course of the year, Analysis Center personnel continued analysis and timely submission of IVS-R4 databases for distribution to the IVS. During the 2012 calendar year, the USNO VLBI Analysis Center produced two VLBI global solutions designated as usn2012a and usn2012b. Earth orientation parameters (EOP) based on this solution and updated by the latest diurnal (IVS-R1 and IVS-R4) experiments were routinely submitted to the IVS. Sinex files based upon the bi-weekly 24-hour experiments were also submitted to the IVS. During the 2012 calendar year, Analysis Center personnel continued a program to use the Very Long Baseline Array (VLBA) operated by the NRAO for the purpose of measuring UT1-UTC. Routine daily 1-hour duration Intensive observations were initiated using the VLBA antennas at Pie Town, NM and Mauna Kea, HI. High-speed network connections to these two antennas are now routinely used for electronic transfer of VLBI data over the Internet to a USNO point of presence. A total of 270 VLBA Intensive experiments were observed and electronically transferred to and processed at USNO in 2012.

Boboltz, David A.↗
DOE OSTI2025

Charge Transfer and Recombination Pathways through Fullerene Guests in Porphyrin-Based MOFs

Porphyrin-based metal–organic frameworks (MOFs) offer a unique platform for building porous donor–acceptor networks that exhibit long-lived charge separation and transport upon incorporation of electron acceptor guest species. Here, in this work, porphyrin-based MOFs, PCN-222(H 2 ) and PCN-222(Zn), synthesized as nanoparticle suspensions, are successfully infiltrated with fullerene acceptor molecules, C 60 or PC 61 BM, in both polar and nonpolar solvent environments. The location and relative binding strength of these guest species are evaluated through a combination of N 2 physisorption measurements, photoluminescence quenching, and UV–vis absorption titration experiments. Semiempirical tight binding calculations are used to screen potential locations of the fullerene guest within the MOF pores, and hybrid density functional theory (DFT)-computed interaction energies confirm the energetically favorable positions. The fundamental photophysics of these donor–acceptor host–guest combinations are probed using ultrafast transient absorption spectroscopy. Sub-picosecond electron transfer involving initial exciplex population is observed, with slow charge recombination lifetimes on the order of τ ~1 ns for all systems in both dimethylformamide and 1,4-dioxane. Charge recombination occurs through population of fullerene and/or framework porphyrin triplet states depending on the porphyrin metalation status. The photophysics of the fullerene-loaded MOFs are discussed in the context of relevant porphyrin–fullerene donor–acceptor molecules to highlight the unique role of the framework environment in dictating photoinduced electron transfer and decay pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Ultrafast photoinduced charge carrier dynamics of L-cysteine and oleylamine stabilized CsPbBr3 perovskite quantum dots coupled with gold nanoparticles

We have synthesized L-cysteine and oleylamine stabilized CsPbBr3 perovskite quantum dots (PQDs) and coupled them with gold nanoparticles (AuNPs). The PQDs and AuNPs, as well as their hybrid nanostructures (HNS), were characterized using UV–visible (UV–vis) and photoluminescence (PL) spectroscopy. The UV–vis spectra show absorption bands of the HNS at 503 and 520 nm, attributed mainly to PQDs and AuNPs, respectively. The PQDs show a strong excitonic PL band peaked at 513 nm from PQDs. The HR-TEM results show the formation of hybrid structures between PQDs and AuNPs, which is also supported by the PL quenching of the PQDs by the coupled AuNPs. Ultrafast dynamics of the exciton and charge carriers in the HNS and pristine PQD were studied using femtosecond transient absorption. Multiexponential fitting of the dynamic data revealed the existence of shallow and deep trap states in pristine PQDs and ultrafast electron transfer from PQDs to AuNPs in the HNS. A kinetic model was proposed to account for the key dynamic processes involved and to extract the time for electron transfer from PQDs to AuNPs in the HNS, found to be ∼2 ps. Dynamic processes in pristine PQDs are largely unchanged by HNS formation with AuNPs.

Chemistry↗
DOE OSTI2025

Spin-Polarized Oxygen Evolution Reaction Enabled by Chiral Molecules Coupled with Ferromagnetic Electrocatalysts

The discovery of chirality-induced spin selectivity (CISS) revolutionized our understanding of the capabilities of chiral molecules, revealing that chiral molecules can function as spin filters, aligning the spin orientation of electrons when they transmit through them. Recently, CISS has been exploited to direct energy conversion, especially the oxygen evolution reaction (OER). However, despite the remarkable progress that has been achieved, the effect of CISS in influencing the intermediate species formation and changing the rate-determining step (RDS) is still vague. To understand those key reaction mechanism steps, electrocatalysts with distinct magnetic characteristics, ferromagnetic CoFe2O4 and paramagnetic Co3O4, were synthesized. The results show that spin-polarized charge carriers retain their spin alignment when coupled with ferromagnetic CoFe2O4, akin to the behavior observed under a magnetic field. The Tafel analysis and kinetic isotope studies (kinetic isotope effect) suggest that in the absence of chiral molecules, the initial electron transfer step, the formation of O* species, governs the rate-determining step (RDS). However, introducing chiral molecules shifts the RDS to a combination of the first and second electron transfers, leading to the formation of OOH*. This conclusion was further supported by in situ infrared spectroscopy, which shows that l-methionine-modified CoFe2O4 (l-CoFe2O4) promotes the formation of OOH*, a key intermediate for O2 generation. This study highlights the critical role of CISS in affecting the OER mechanism and intermediate species formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Exploring the Photogenerated Charge Transfer Mechanism in Cu 2 O@MoS 2 Heterojunction Photocatalyst Using Transient Absorption Spectroscopy

Both heterojunction and core–shell photocatalysts have demonstrated promising performance in photocatalytic CO 2 conversions to fuels. However, fundamental knowledge of heterojunctions in core–shell structures is highly desired to facilitate the design of future photocatalysts. By combining advanced experimental characterizations and density functional theory (DFT) calculations, the role of the Cu 2 O@MoS 2 heterojunction in photocatalytic CO 2 conversions to fuels was investigated. We discovered that the charge dynamics and electron transfer properties of Cu2O@MoS 2 photocatalysts are altered by the heterojunction and Cu 2 O underlayer due to the electron transfer from Cu 2 O to MoS 2 and the change in CO 2 adsorption strength on the hybrid catalyst surface. Consequently, more electrons can travel to the surrounding liquid environment to be consumed by CO 2 reduction. This study provides experimental and theoretical investigations of the fundamental mechanisms of heterojunction core–shell photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Electronic energy transfer and quenching in copolymers of styrene and 2-(2-prime-hydroxy -5-prime-vinylphenyl)-2H-benzotriazole Photochemical processes in polymeric systems. X

Intensity and lifetime quenching of the polystyrene monomer and excimer fluorescence emission by a pendant quencher have been studied in the solid state and in solution for a series of copolymers of styrene and 2-(2-prime-hydroxy-5-prime-vinylphenyl)-2H-benzotriazole. Two mechanisms of quenching have been identified. One involves interception of the migrating monomer excitation by the quencher, and the other involves a single-step Foerster energy-transfer process from the excimer traps to a quencher. The relative efficiencies of these two quenching mechanisms in the solid state and in solution have been compared and related to the efficiency of electronic energy migration. An estimate of the excimer trap concentration in solid polystyrene is also reported.

Coulter, D. R.↗
DOE OSTI2024

Manipulating symmetry-breaking charge separation employing molecular recognition

The exploration of symmetry-breaking charge separation (SB-CS) is imperative when designing functional light-harvesting materials. Past explorations, however, have been confined to covalent systems, more often than not requiring complicated/demanding syntheses and facing inconvenient regulation of charge transfer processes. Here, in this work, we present a concept that regulates the efficiency of SB-CS through molecular recognition utilizing a pyridinium-based cyclophane as a host. This host undergoes photo-driven excited-state SB-CS. By employing different guests with distinct frontier molecular orbital energy levels, we have achieved comprehensive control of electron transfer pathways in the cyclophane, modulating between accelerated (>10-fold) intramolecular SB-CS involving superexchange and direct intermolecular electron transfer between the host and guest. The improvement in SB-CS efficiency results in catalytic activity for the photo-oxidation of a sulfur-mustard simulant. This research offers an opportunity for tuning SB-CS by utilizing molecular recognition, which holds the potential for achieving precise regulation without complicated organic syntheses.

charge transfer↗
DOE OSTI2024

Circumventing Kinetic Barriers to Metal Hydride Formation with Metal–Ligand Cooperativity

We report the two-electron, one-proton mechanism of cobalt hydride formation for the conversion of [Co III Cp(P Ph 2 N Bn 2 )(CH 3 CN)] 2+ to [HCo III Cp(P Ph 2 NBn 2 )] + . This complex catalytically converts CO 2 to formate under CO 2 reduction conditions, with hydride formation as a key elementary step. Through a combination of electrochemical measurements, digital simulations, theoretical calculations, and additional mechanistic and thermochemical studies, we outline the explicit role of the P Ph 2 N Bn 2 ligand in the proton-coupled electron transfer (PCET) reactivity that leads to hydride formation. We reveal three unique PCET mechanisms, and we show that the amine on the P Ph 2 N Bn 2 ligand serves as a kinetically accessible protonation site en route to the thermodynamically favored cobalt hydride. Cyclic voltammograms recorded with proton sources that span a wide range of pK a values show four distinct regimes where the mechanism changes as a function of acid strength, acid concentration, and timescale between electrochemical steps. Peak shift analysis was used to determine proton transfer rate constants where applicable. Furthermore, this work highlights the astute choices that must be made when designing catalytic systems, including the basicity and kinetic accessibility of protonation sites, acid strength, acid concentration, and timescale between electron transfer steps, to maximize catalyst stability and efficiency.

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

In Situ Characterization of Surface Recombination in p-Si/SiO x Based Photoelectrochemical Cells

Time-resolved infrared (TRIR) and electrochemical impedance spectroscopy (EIS) were utilized to quantify surface states present at silicon oxide (SiO x ) protected crystalline p-Si electrolyte interfaces. The primary goal was to identify p-Si/SiO x photoelectrodes with both low surface recombination rates and efficient multi-electron transfer to an acceptor present in the external electrolyte. Three SiO x layers were investigated: native oxide (nOx), chemical oxide (cOx), and rapid thermal annealed (RTA) thermal oxide (tOx). Comparative study with [Ru(bpy) 3 ](PF 6 ) 2 as the electron acceptor indicated that tOx was most optimal with a small effective recombination rate, multi-electron transfer capability, and photovoltage of 500 ± 50 mV. A secondary goal was to analyze the surface recombination rates with the Shockley–Read–Hall (SRH) kinetic model. Two surface states were identified from this analysis, one closer to the CB edge (V t,1 ) and the other near the midgap (V t,2 ). EIS and SRH analyses revealed that a forming gas (5% H 2 /N 2 ) anneal (FGA) decreased surface recombination for tOx and nOx through a lower density of surface states. In the case of tOx, the infrared data indicated that V t,2 was completely removed. Here, the energetic positions of the band edges were correlated with the surface state density; low densities corresponded to more favorable potentials for inversion layer formation, which is expected to be most optimal for photocatalysis. Collectively this study indicates that the free carrier dynamics provided by TRIR represent a powerful in situ probe of the band edge and the surface state energetics in silicon based photoelectrochemical cells.

Electrochemical Impedance Spectroscopy↗
DOE OSTI2026

Kinetics vs Thermodynamics: Engineering Photoredox Reactivity from an Upper Excited State of Fe II

Ultrafast deactivation of metal-to-ligand charge-transfer (MLCT) states into low-lying metal-centered states has long limited the utility of first-row transition-metal complexes in a broad range of applications, including photoredox catalysis. Here we bypass such limitations using a Fe II -pyridinium carbene complex to enable electron transfer reactivity directly from a higher-lying MLCT state. Time-resolved spectroscopic data revealed that the higher-energy MLCT manifold relaxes to lower-lying metal-centered states with a time constant of ca. 3 ps. The nature of the metal-centered (MC) excited state as a 3 MC (i.e., S = 1) was inferred from variable-temperature transient absorption studies. These experiments also revealed that the ground-state recovery process occurs at or very near the “Marcus barrierless regime”, thereby allowing for an estimate of its excited-state redox potential. The detailed picture of the energetics of this compound that emerged enabled fine-tuning of competing thermodynamic and kinetic pathways to effect electron transfer from the higher-energy MLCT excited state prior to relaxation to the ligand-field manifold. We believe these results open an unexplored landscape for the use of earth-abundant first-row transition-metal-based chromophores for applications in light-to-chemical energy conversion.

charge transfer↗
NASA NTRS1997

Energy from Redox Disproportionation of Sugar Carbon Drives Biotic and Abiotic Synthesis

To identify the energy source that drives the biosynthesis of amino acids, lipids, and nucleotides from glucose, we calculated the free energy change due to redox disproportionation of the substrate carbon of: (1) 26-carbon fermentation reactions and (2) the biosynthesis of amino acids and lipids of E. coli from glucose. The free energy (cal/mmol of carbon) of these reactions was plotted as a function of the degree of redox disproportionation of carbon (disproportionative electron transfers (mmol)/mmol of carbon). The zero intercept and proportionality between energy yield and degree of redox disproportionation exhibited by this plot demonstrate that redox disproportionation is the principal energy source of these redox reactions (slope of linear fit = -10.4 cal/mmol of disproportionative electron transfers). The energy and disproportionation values of E. coli amino acid and lipid biosynthesis from glucose lie near this linear curve fit with redox disproportionation accounting for 84% and 96% (and ATP only 6% and 1 %) of the total energy of amino acid and lipid biosynthesis, respectively. These observations establish that redox disproportionation of carbon, and not ATP, is the primary energy source driving amino acid and lipid biosynthesis from glucose. In contrast, we found that nucteotide biosynthesis involves very little redox disproportionation, and consequently depends almost entirely on ATP for energy. The function of sugar redox disproportionation as the major source of free energy for the biosynthesis of amino acids and lipids suggests that sugar disproportionation played a central role in the origin of metabolism, and probably the origin of life.

Weber, Arthur L.↗
NASA NTRS1997

Energy from Redox Disproportionation of Sugar Carbon Drives Biotic and Abiotic Synthesis

To identify the energy source that drives the biosynthesis of amino acids, lipids, and nucleotides from glucose, we calculated the free energy change due to redox disproportionation of the substrate carbon of: (1) 26-carbon fermentation reactions and (2) the biosynthesis of amino acids and lipids of E. coli from glucose. The free energy (cal/mmol of carbon) of these reactions was plotted as a function of the degree of redox disproportionation of carbon (disproportionative electron transfers (mmol)/mmol of carbon). The zero intercept and proportionality between energy yield and degree of redox disproportionation exhibited by this plot demonstrate that redox disproportionation is the principal energy source of these redox reactions (slope of linear fit = -10.4 cal/mmol of disproportionative electron transfers). The energy and disproportionation values of E. coli amino acid and lipid biosynthesis from glucose lie near this linear curve fit with redox disproportionation accounting for 84% and 96% (and ATP only 6% and 1%) of the total energy of amino acid and lipid biosynthesis, respectively. These observations establish that redox disproportionation of carbon, and not ATP, is the primary energy source driving amino acid and lipid biosynthesis from glucose. In contrast, we found that nucleotide biosynthesis involves very little redox disproportionation, and consequently depends almost entirely on ATP for energy. The function of sugar redox disproportionation as the major source of free energy for the biosynthesis of amino acids and lipids suggests that sugar disproportionation played a central role in the origin of metabolism, and probably the origin of life.

Weber, Arthur L.↗
NASA NTRS1989

Information storage at the molecular level - The design of a molecular shift register memory

The control of electron transfer rates is discussed and a molecular shift register memory at the molecular level is described. The memory elements are made up of molecules which can exist in either an oxidized or reduced state and the bits can be shifted between the cells with photoinduced electron transfer reactions. The device integrates designed molecules onto a VLSI substrate. A control structure to modify the flow of information along a shift register is indicated schematically.

Beratan, David N.↗
NASA NTRS1982

Electronic levels and charge distribution near the interface of nickel

The energy levels in clusters of nickel atoms were investigated by means of a series of cluster calculations using both the multiple scattering and computational techniques (designated SSO) which avoids the muffin-tin approximation. The point group symmetry of the cluster has significant effect on the energy of levels nominally not occupied. This influences the electron transfer process during chemisorption. The SSO technique permits the approaching atom or molecule plus a small number of nickel atoms to be treated as a cluster. Specifically, molecular levels become more negative in the O atom, as well as in a CO molecule, as the metal atoms are approached. Thus, electron transfer from the nickel and bond formation is facilitated. This result is of importance in understanding chemisorption and catalytic processes.

Waber, J. T.↗
NASA NTRS2012

Near-Infrared Photon-Counting Camera for High-Sensitivity Observations

The dark current of a transferred-electron photocathode with an InGaAs absorber, responsive over the 0.9-to-1.7- micron range, must be reduced to an ultralow level suitable for low signal spectral astrophysical measurements by lowering the temperature of the sensor incorporating the cathode. However, photocathode quantum efficiency (QE) is known to reduce to zero at such low temperatures. Moreover, it has not been demonstrated that the target dark current can be reached at any temperature using existing photocathodes. Changes in the transferred-electron photocathode epistructure (with an In- GaAs absorber lattice-matched to InP and exhibiting responsivity over the 0.9- to-1.7- m range) and fabrication processes were developed and implemented that resulted in a demonstrated >13x reduction in dark current at -40 C while retaining >95% of the approximately equal to 25% saturated room-temperature QE. Further testing at lower temperature is needed to confirm a >25 C predicted reduction in cooling required to achieve an ultralow dark-current target suitable for faint spectral astronomical observations that are not otherwise possible. This reduction in dark current makes it possible to increase the integration time of the imaging sensor, thus enabling a much higher near-infrared (NIR) sensitivity than is possible with current technology. As a result, extremely faint phenomena and NIR signals emitted from distant celestial objects can be now observed and imaged (such as the dynamics of redshifting galaxies, and spectral measurements on extra-solar planets in search of water and bio-markers) that were not previously possible. In addition, the enhanced NIR sensitivity also directly benefits other NIR imaging applications, including drug and bomb detection, stand-off detection of improvised explosive devices (IED's), Raman spectroscopy and microscopy for life/physical science applications, and semiconductor product defect detection.

Jurkovic, Michael↗
DOE OSTI2024

Competitive Valerate Binding Enables RuO 2 -Mediated Butene Electrosynthesis in Water

The (non)-Kolbe oxidation of valeric acid, sourced from a hydrolysis product of cellulose, provides a sustainable synthetic route to access value-added products, such as butene. An essential mechanistic step preceding product formation involves the oxidative and decarboxylative cleavage of a C–C bond. Yet, the role of the electrode surface in mediating this oxidative step remains an open question: the electron transfer can occur either via an inner-sphere or outer-sphere mechanism. Here, we report the electrochemical, in situ spectroscopic, computational, and reactivity studies of RuO 2 -mediated oxidative decarboxylation of valeric acid to butene in aqueous electrolytes. We find that carboxylates bind to RuO 2 anode surfaces at potential values where decarboxylation products are observed. Our results are consistent with a reaction scheme where the competitive and catalytic oxygen evolution reaction (OER) is impeded by these bound carboxylate species while these species are inert toward butene formation. Our results implicate an outer-sphere electron transfer mechanism for decarboxylation where the surface chemistry of the RuO 2 electrode serves to enable higher non-Kolbe reaction selectivity by suppressing the parasitic OER. Furthermore, our findings delineate interfacial design principles for selective electrochemical systems that utilize water as the ultimate oxidant for sustainable decarboxylation.

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

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗