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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 1,279 records · Page 71
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Trigonal Bipyramidal V 3+ Complex as an Optically Addressable Molecular Qubit Candidate

Synthetic chemistry enables a bottom-up approach to quantum information science, where atoms can be deterministically positioned in a quantum bit or qubit. Two key requirements to realize quantum technologies are qubit initialization and read-out. By imbuing molecular spins with optical initialization and readout mechanisms, analogous to solid-state defects, molecules could be integrated into existing quantum infrastructure. To mimic the electronic structure of optically addressable defect sites, we designed the spin-triplet, V 3+ complex, (C 6 F 5 ) 3 trenVCN t Bu (1).We measured the static spin properties as well as the spin coherence time of1demonstrating coherent control of this spin qubit with a 240 GHz electron paramagnetic resonance spectrometer powered by a free electron laser. We found that1exhibited narrow, near-infrared photoluminescence (PL) from a spin-singlet excited state. Using variable magnetic field PL spectroscopy, we resolved emission into each of the ground-state spin sublevels, a crucial component for spin-selective optical initialization and readout. This work demonstrates that trigonally symmetric, heteroleptic V 3+ complexes are candidates for optical spin addressability.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Revisiting Understanding of Electrochemical CO 2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory

Copper (Cu) electrodes, as the most efficacious of CO 2 reduction reaction (CO 2 RR) electrocatalysts, serve as prototypes for determining and validating reaction mechanisms associated with electrochemical CO 2 reduction to hydrocarbons. As in situ electrochemical mechanism determination by experiments is still out of reach, such mechanistic analysis typically is conducted using density functional theory (DFT). The semilocal exchange-correlation (XC) approximations most often used to model such catalysis unfortunately engender a basic error: predicting the wrong adsorption site for CO (a key CO 2 RR intermediate) on the most ubiquitous facet of Cu, namely, Cu(111). This longstanding inconsistency casts lingering doubt on previous DFT predictions of the attendant CO 2 RR kinetics. Here, we apply embedded correlated wavefunction (ECW) theory, which corrects XC functional error, to study the CO 2 RR on Cu(111) via both surface hydride (*H) transfer and proton-coupled electron transfer (PCET). We predict that adsorbed CO (*CO) reduces almost equally to two intermediates, namely, hydroxymethylidyne (*COH) and formyl (*CHO) at –0.9 V vs the RHE. In contrast, semilocal DFT approximations predict a strong preference for *COH. With increasing applied potential, the dominance of *COH (formed via potential-independent surface *H transfer) diminishes, switching to the competitive formation of both *CHO and *COH (both formed via potential-dependent PCET). Furthermore, our results also demonstrate the importance of including explicitly modeled solvent molecules in predicting electron-transfer barriers and reveal the pitfalls of overreliance on simple surface *H transfer models of reduction reactions.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

Highly Active Hydrogen Evolution Reaction (HER) Catalysts Formed by Energetic Pt n Cluster Deposition: Deposition Dynamics and the HER Mechanism

Mass-selected Pt n + (n ≤ 7) were deposited at variable energies on highly oriented pyrolytic graphite (HOPG), creating highly active hydrogen evolution reaction (HER) electrocatalysts. HER mass activities were ~2 to >10 times higher than those for the surface atoms in bulk Pt and for Pt n deposited on several other supports. Thus, high activity reflects the Pt-C structures formed by energetic Pt n -HOPG impacts, in addition to high Pt surface availability. The Pt n /HOPG electrodes were probed by X-ray photoelectron spectroscopy, low energy ion scattering, and electron microscopy. Born-Oppenheimer molecular dynamics (BOMD) was used to simulate Pt n - HOPG impacts, revealing the types of structures formed at different energies, then DFT was used to probe their most important HER pathways. For low deposition energies, the Pt n deposit onto the HOPG surface with sub-unit sticking probability, aggregating at defects. With increasing deposition energy, the sticking probability initially decreases, then rises to unity as subplantation and defect creation allow formation of strongly bonded platinum-carbon structures. Barriers for HER on these structures were found to be low and weakly dependent on Pt n size, consistent with experiment. The activities were highest for small covalently-bonded Pt-C structures created at high deposition energies. The larger aggregated structures formed at low energies were less active, but still substantially better than the bulk Pt surface monolayer. The catalysts were stable in repeated potential cycling at reducing potentials, but electrodes containing subplanted Pt became more active when scanned to oxidizing potentials, due to emergence of subplanted Pt onto the surface.

08 HYDROGEN↗
DOE OSTI2026

Pressurized Gas-Driven Elemental Redistribution Enables Ultrastable PtNi Catalysts for Heavy-Duty Vehicles

Gas-driven element redistribution, characterized by the preferential enrichment of one element at the surface relative to the bulk, is frequently observed in multicomponent alloys. Using L1 0 -ordered PtNi as a model system, we reveal that gas pressure plays a critical role in governing adsorption-driven surface composition during annealing in reducing gases: low pressure favors Pt surface segregation, while high pressure facilitates Ni surface enrichment. In this study, we developed a high-pressure nitriding (HPN) strategy that modulates the surface structure and composition of PtNi catalysts. The resulting HPN-PtNi exhibits enhanced performance and durability in membrane electrode assemblies for heavy-duty fuel cell applications, maintaining a high current density of 1.19 A cm −2 at 0.7 V after 90,000 voltage cycles. Through a combination of experimental and theoretical analyses, we reveal that the HPN process forms additional stabilizing Ni−N bonds and induces elemental redistribution with Ni surface enrichment and a Ni-deficient Pt subsurface. These modifications alter the atomic coordination environment of the ordered PtNi phase. This work presents a generalizable strategy to design robust and high-performing Pt-based catalysts by controlling gas-pressure-driven elemental redistribution and dopant incorporation.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2016

Enhancing perovskite electrocatalysis through strain tuning of oxygen deficiency

Oxygen vacancies in transition-metal oxides facilitate catalysis critical for energy storage and generation. However, promoting vacancies at the lower temperatures required for operation in devices such as metal–air batteries and portable fuel cells has proven elusive. Here we used thin films of perovskite-based strontium cobaltite (SrCoO x ) to show that epitaxial strain is a powerful tool for manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen-deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite’s catalytic activity toward this important reaction by over an order of magnitude, equaling that of precious-metal catalysts, including IrO2. Lastly, our findings demonstrate that strain in these oxides can dictate the oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2011

Platinum Supported on NbRuyOz as Electrocatalyst for Ethanol Oxidation in Acid and Alkaline Fuel Cells

Platinum supported on a mixed metal oxide, NbRu{sub y}O{sub z} (8Nb:1Ru), was evaluated as an electrocatalyst for the ethanol oxidation reaction (EOR) in 0.1 M HClO{sub 4} and 1 M KOH. The support was synthesized from a liquid precursor solution of metal chlorides that was aerosolized and thermally decomposed into a powder via the spray pyrolysis (SP) process. Two samples were of primary interest: 30%Pt deposited onto the support by dry impregnation and 60%Pt as part of the precursor solution that underwent in situ SP Pt dispersion. TEM, SEM, and XRD were used to confirm morphology and deposition of Pt. XPS and XAS studies confirmed elemental distribution and oxidation state of Pt catalyst. In situ IRRAS studies in 0.1 M HClO{sub 4} show that these electrocatalysts are capable of facilitating the complete oxidation pathway of EOR, involving scission of the C-C bond and CO oxidation.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2011

Carbon-Supported IrNi Core-Shell Nanoparticles: Synthesis Characterization and Catalytic Activity

We synthesized carbon-supported IrNi core-shell nanoparticles by chemical reduction and subsequent thermal annealing in H{sub 2}, and verified the formation of Ir shells on IrNi solid solution alloy cores by various experimental methods. The EXAFS analysis is consistent with the model wherein the IrNi nanoparticles are composed of two-layer Ir shells and IrNi alloy cores. In situ XAS revealed that the Ir shells completely protect Ni atoms in the cores from oxidation or dissolution in an acid electrolyte under elevated potentials. The formation of Ir shell during annealing due to thermal segregation is monitored by time-resolved synchrotron XRD measurements, coupled with Rietveld refinement analyses. The H{sub 2} oxidation activity of the IrNi nanoparticles was found to be higher than that of a commercial Pt/C catalyst. This is predominantly due to Ni-core-induced Ir shell contraction that makes the surface less reactive for IrOH formation, and the resulting more metallic Ir surface becomes more active for H{sub 2} oxidation. This new class of core-shell nanoparticles appears promising for application as hydrogen anode fuel cell electrocatalysts.

08 HYDROGEN↗
DOE OSTI2011

Unveiling N-Protonation and Anion-Binding Effects on Fe/N/C Catalysts for O2 Reduction in Proton-Exchange-Membrane Fuel Cells

The high cost of proton-exchange-membrane fuel cells would be considerably reduced if platinum-based catalysts were replaced by iron-based substitutes, which have recently demonstrated comparable activity for oxygen reduction but whose cause of activity decay in acidic medium has been elusive. Here, we reveal that the activity of Fe/N/C catalysts prepared through a pyrolysis in NH{sub 3} is mostly imparted by acid-resistant FeN{sub 4} sites whose turnover frequency for the O{sub 2} reduction can be regulated by fine chemical changes of the catalyst surface. We show that surface N-groups protonate at pH 1 and subsequently bind anions. This results in decreased activity for the O{sub 2} reduction. The anions can be removed chemically or thermally, which restores the activity of acid-resistant FeN{sub 4} sites. These results are interpreted as an increased turnover frequency of FeN{sub 4} sites when specific surface N-groups protonate. These unprecedented findings provide a new perspective for stabilizing the most active Fe/N/C catalysts known to date.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2011

Degradation of Ionic Pathway in PEM Fuel Cell Cathode

The degradation of the ionic pathway throughout the catalyst layer in proton exchange membrane fuel cells was studied under an accelerated stress test of catalyst support (potential hold at 1.2 V). Electrochemical behaviors of the cathode based on graphitic mesoporous carbon supported Pt catalyst were examined using electrochemical impedance spectroscopy and cyclic voltammetry. Impedance data were plotted and expressed in the complex capacitance form to determine useful parameters in the transmission line model: the double-layer capacitance, peak frequency, and ionic resistance. Electrochemical surface area and hydrogen crossover current through the membrane were estimated from cyclic voltammogram, while cathode Faradaic resistance was compared with ionic resistance as a function of test time. It was observed that during an accelerated stress test of catalyst support, graphitic mesoporous carbon becomes hydrophilic which increases interfacial area between the ionomer and the catalyst up to 100 h. However, the ionic resistance in the catalyst layer drastically increases after 100 h with further carbon support oxidation. The underlying mechanism has been studied and it was found that significant degradation of ionic pathway throughout the catalyst layer due to catalyst support corrosion induces uneven hydration and mechanical stress in the ionomer.

08 HYDROGEN↗
DOE OSTI2012

Radiation-Induced Reduction of Ceria in Single and Polycrystalline Thin Films

Ceria (CeO{sub 2}) is a technologically important ceramic material with a wide range of neoteric applications in catalysis, solid oxide fuel cells, oxygen gas sensors, hydrogen production, and ultraviolet shielding. Recent research has revealed promising biomedical applications of ceria. Nanoparticles of ceria have been shown to protect healthy cells from radiation-induced cellular damage. The mechanisms governing the radioprotection characteristics of ceria nanoparticles are not well understood and it has been hypothesized that reversible switching between Ce{sup 4+} and Ce{sup 3+} states may enable ceria nanoparticles to mop up free radicals.

08 HYDROGEN↗
DOE OSTI2012

A Comparative Ab Initio Study of the Primary Hydration and Proton Dissociation of Various Imide and Sulfonic Acid Ionomers

We compare the role of neighboring group substitutions on proton dissociation of hydrated acidic moieties suitable for proton exchange membranes through electronic structure calculations. Three pairs of ionomers containing similar electron withdrawing groups within the pair were chosen for the study: two fully fluorinated sulfonyl imides (CF3SO2NHSO2CF3 and CF3CF2SO2NHSO2CF3), two partially fluorinated sulfonyl imides (CH3SO2NHSO2CF3 and C6H5SO2NHSO2CF2CF3), and two aromatic sulfonic acid based material s (CH3C6H4SO3H and CH3 OC6 - H3OCH3C6H4SO3H). Fully optimized counterpoise (CP) corrected geometries were obtained for each ionomer fragment with the inclusion of water molecules at the B3LYP/6-311G** level of density functional theory. Spontaneous proton dissociation was observed upon addition of three water molecules in each system, and the transition to a solvent-separated ion pair occurred when four water molecules were introduced. No considerable quantitative or qualitative differences in proton dissociation, hydrogen bond networks formed, or water binding energies were found between systems containing similar electron withdrawing groups. Each of the sulfonyl imide ionomers exhibited qualitatively similar results regarding proton dissociation and separation. The fully fluorinated sulfonyl imides, however, showed a greater propensity to exist in dissociated and ion-pair separated states at low degrees of hydration than the partially fluorinated sulfonyl imides. This effect is due to the additional electron withdrawing groups providing charge stabilization as the dissociated proton migrates away from the imide anion.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2012

Multiscale simulation on a light-harvesting molecular triad

Here, we have investigated the effect of solvation and confinement on an artificial photosynthetic material, carotenoid-porphyrin-C60 molecular triad, by a multiscale approach and an enhanced sampling technique. We have developed a combined approach of quantum chemistry, statistical physics, and all-atomistic molecular dynamics simulation to determine the partial atomic charges of the ground-state triad. To fully explore the free energy landscape of triad, the replica exchange method was applied to enhance the sampling efficiency of the simulations. The confinement effects on the triad were modeled by imposing three sizes of spherocylindrical nanocapsules. The triad is structurally flexible under ambient conditions, and its conformation distribution is manipulated by the choice of water models and confinement. Two types of water models (SPC/E and TIP3P) are used for solvation. When solvated by SPC/E water, whose HOH angle follows an ideal tetrahedron, the structural characteristics of triad is compact in the bulk systems. However, under a certain nanosized confinement that drastically disrupts hydrogen bond networks in solvent, the triad favors an extended configuration. By contrast, the triad solvated by TIP3P water shows a set of U-shaped conformations in the confinement. We have shown that a slight structural difference in the two water models with the same dipole moment can have great distinction in water density, water orientation, and the number of hydrogen bonds in the proximity of a large flexible compound such as the triad. Subsequently, it has direct impact on the position of the triad in a confinement as well as the distribution of conformations at the interface of liquid and solid in a finite-size system.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2014

Hydroxide Degradation Pathways for Imidazolium Cations. A DFT Study

Imidazolium cations are promising candidates as covalently tetherable cations for application in anion exchange membranes. They have generated specific interest in alkaline membrane fuel cell applications where ammonium-based cations have been the most commonly applied but have been found to be susceptible to hydroxide attack. In the search for high stability cations, a detailed understanding of the degradation pathways and reaction barriers is required. In this work, we investigate imidazolium and benzimidazolium cations in the presence of hydroxide using density functional theory calculations for their potential in alkaline membrane fuel cells. Moreover, the dominant degradation pathway for these cations is predicted to be the nucleophilic addition–elimination pathway at the C-2 atom position on the imidazolium ring. Steric interferences, introduced by substitutions at the C-2, C-4, and C-5 atom positions, were investigated and found to have a significant, positive impact on calculated degradation energy barriers. Benzimidazolium cations, with their larger conjugated systems, are predicted to degrade much faster than their imidazolium counterparts. Our results provide important insight into designing stable cations for anion exchange membranes. Some of the molecules studied have significantly increased degradation energy barriers suggesting that they could possess significantly improved (several orders of magnitude) durability compared to traditional cations and potentially enable new applications.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2014

CO 2 Adsorption on Anatase TiO 2 (101) Surfaces in the Presence of Subnanometer Ag/Pt Clusters: Implications for CO 2 Photoreduction

We show how CO 2 adsorption on perfect and reduced anatase TiO 2 (101) surfaces can be substantially modified by the presence of surface Ag and Pt octamer clusters, using density functional theory calculations. Furthermore, we found that adsorption was affected even at sites where the adsorbate was not in direct contact with the octamer, which we attributed to charge donation to CO 2 from the Ag/Pt-modified surface, as well as an electrostatic competition between attractive (Ti–O) and repulsive (Ti–C) interactions. Additionally, TiO 2 -supported Pt octamers offer key advantages that could be leveraged for CO 2 photoreduction, including providing additional stable adsorption sites for bent CO 2 species and facilitating charge transfer to aid in CO 2 – anion formation. Electronic structure analysis suggests these factors arise primarily from the hybridization of the bonding molecular orbitals of CO 2 with d orbitals of the Pt atoms. Our results show that, for adsorption on TiO 2 -supported Pt octamers, the O–C–O bending and C–O asymmetric stretching frequencies can be used as reliable indicators of the presence of the CO 2 – anion intermediate as well as to distinguish unique adsorption geometries or sites. Finally, we suggest a possible pathway for subsequent CO 2 dissociation to CO at the surface of a reduced anatase TiO 2 (101)-supported Pt octamer, which has a computed energy barrier of 1.01 eV.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2014

Persistent Subdiffusive Proton Transport in Perfluorosulfonic Acid Membranes

Proton transport (PT) in solutions of small amphiphiles in water has previously been shown to be subdiffusive for long times. The present study analyzes simulations of hydrated perfluorosulfonic acid (PFSA) membranes in order to determine whether PT is also subdiffusive in these important amphiphilic systems. Here, we show that PT is indeed subdiffusive for several hundred picoseconds for all hydration levels examined, and the subdiffusive behavior is highly dependent on water concentration. We also investigate the caging of the excess proton using a recently developed technique and show that the excess proton exhibits caging effects up to at least 1 ns in PFSA systems. In order to fully characterize the long-time behavior of PT in PFSAs, these results demonstrate that multiple nanosecond trajectories are needed, well beyond the current capabilities of ab initio molecular dynamics.

25 ENERGY STORAGE↗
DOE OSTI2011

Isothermal Ice Crystallization Kinetics in the Gas-Diffusion Layer of a Proton-Exchange-Membrane Fuel Cell

Nucleation and growth of ice in the fibrous gas-diffusion layer (GDL) of a proton-exchange membrane fuel cell (PEMFC) are studied using isothermal differential scanning calorimetry (DSC). Isothermal crystallization rates and pseudo-steady-state nucleation rates are obtained as a function of subcooling from heat-flow and induction-time measurements. Kinetics of ice nucleation and growth are studied at two polytetrafluoroethylene (PTFE) loadings (0 and 10 wt %) in a commercial GDL for temperatures between 240 and 273 K. A nonlinear ice-crystallization rate expression is developed using Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory, in which the heat-transfer-limited growth rate is determined from the moving-boundary Stefan problem. Induction times follow a Poisson distribution and increase upon addition of PTFE, indicating that nucleation occurs more slowly on a hydrophobic fiber than on a hydrophilic fiber. The determined nucleation rates and induction times follow expected trends from classical nucleation theory. Finally, a validated rate expression is now available for predicting ice-crystallization kinetics in GDLs.

30 DIRECT ENERGY CONVERSION↗