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Results for “selective doping”

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 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Patterning a π-conjugated polyelectrolyte through sequential polymerization of a bifunctional ionic liquid monomer

An electronically conductive polyelectrolyte is prepared by the sequential polymerization of a bifunctional imidazolium-based ionic liquid (IL) monomer, composed of a thienyl and vinyl containing cation paired with a tetrafluoroborate anion. In the first step, potentiodynamic electropolymerization of the thienyl moiety forms a cationic polyalkylthiophene that is soluble in select organic solvents. Cyclic voltammetry (CV) was used to determine the polymer p-doping potential (0.31 V) and the bipolaronic state (1.49 V). The polymer exhibits electrochromism, converting from red in the neutral state (lambda(max) = 443 nm) to dark blue in the polaronic state (lambda(max) = 819 nm). The solution-processable polymer can be cast into a film, masked and patterned by UV-initiated free radical polymerization of the vinyl moiety. Small-angle X-ray scattering (SAXS) revealed that the insoluble crosslinked polyalkylthiophene-polyvinylimidazolium adopts a lamellar structure with a lattice spacing of 3.3 nm. Four-probe d.c. conductivity measurements determined the de-doped electrical conductivity was 1.0 x 10(-2) S/cm. The results underscore the importance of the anion in controlling the polymerization of IL monomers.

Ionic liquid↗
DOE OSTI2019

Elucidating Interfacial Phenomena between Solid-State Electrolytes and the Sulfur-Cathode of Lithium–Sulfur Batteries

Sulfide solid-state electrolytes are promising materials to be used in Li–S batteries because they have the potential to mitigate some of the challenges currently faced by this technology such as the dissolution of polysulfide species and the flammability of conventional organic-based electrolytes. Nevertheless, the electrode/electrolyte interfaces are not well-understood yet. In this study, we use density functional theory and ab initio molecular dynamics simulations to investigate the formation of the cathode–electrolyte interface at two limiting states of charge: S 8 and Li 2 S. β-Li 3 PS 4 and two lithium halide-doped sulfides (Li 6 PS 5 Cl and Li 7 P 2 S8I) were selected because of their Li-ion superionic conductivity and compatibility with sulfur electrodes. The work of adhesion and interfacial energy of the interfaces were calculated as descriptors of the interfacial properties, and then the mechanisms of the interfacial reactions taking place were characterized. Lastly, a charge transfer analysis is presented, suggesting that, overall, the S 8 electrode will oxidize the electrolyte, whereas the fully discharged Li 2 S cathode will reduce it at different extents depending on the reactivity of the exposed facet.

25 ENERGY STORAGE↗
DOE OSTI2025

Promotional Effect of ZnO and ZrO 2 in K-Doped Fe Catalysts for CO 2 Hydrogenation to Light Olefins

Promoters play a critical role in tuning the activity and selectivity of Fe catalysts in CO 2 hydrogenation to produce light olefins, which are key building blocks in the petrochemical industry. Herein, by a combined experimental and theoretical approach, we show that high and stable performance of Fe catalysts could be achieved by taking advantage of the promotional effect of both Zn and Zr. Structural characterization indicates that ZnO could improve the dispersion and reducibility of Fe oxides and facilitate the formation of active Fe carbide species, whereas ZrO 2 could stabilize the structure and catalytic performance, especially the selectivity of hydrocarbon products. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments suggest that carbonate, bicarbonate, formate, and methoxy are essential intermediates in the CO 2 hydrogenation to hydrocarbon products, including paraffins and olefins. The conversion kinetics of each intermediate species are dependent on the type of promoters as well as the phase structure of the active Fe species. DFT calculations revealed a strong correlation between the formation energy of surface oxygen vacancies and that of Fe carbide species in promoted Fe oxides, in accordance with experimental results. Moreover, the calculated energy profiles of CO 2 hydrogenation over different catalysts indicate that Zn could promote the activation of CO 2 and its transformation to the oxygenate intermediates, while Zr could facilitate the conversion of oxygenates to hydrocarbon precursors. Finally, the discrepancies in the evolution trend of various intermediate species on promoted Fe catalysts in the transient DRIFTS experiments can be rationalized by the differences in energy barriers of elementary or rate limiting steps.

CO2 conversion↗
DOE OSTI2021

Superior photo-carrier diffusion dynamics in organic-inorganic hybrid perovskites revealed by spatiotemporal conductivity imaging

Abstract The outstanding performance of organic-inorganic metal trihalide solar cells benefits from the exceptional photo-physical properties of both electrons and holes in the material. Here, we directly probe the free-carrier dynamics in Cs-doped FAPbI 3 thin films by spatiotemporal photoconductivity imaging. Using charge transport layers to selectively quench one type of carriers, we show that the two relaxation times on the order of 1 μs and 10 μs correspond to the lifetimes of electrons and holes in FACsPbI 3 , respectively. Strikingly, the diffusion mapping indicates that the difference in electron/hole lifetimes is largely compensated by their disparate mobility. Consequently, the long diffusion lengths (3~5 μm) of both carriers are comparable to each other, a feature closely related to the unique charge trapping and de-trapping processes in hybrid trihalide perovskites. Our results unveil the origin of superior diffusion dynamics in this material, crucially important for solar-cell applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Supramolecular assemblies of polybenzimidazole and aromatic polycarboxylic acids with superior mechanical and H 2 /CO 2 separation properties

Aromatic polycarboxylic acids complex with imidazoles, forming supramolecular assemblies. Herein, we demonstrate that polybenzimidazole (PBI) can be augmented by aromatic polycarboxylic acids, including phthalic acid (PA), trimesic acid (TMA), and pyromellitic acid (PMA), and the resulting supramolecular assemblies exhibit attractive H 2 /CO 2 separation performance for precombustion carbon capture. The acid doping decreases the free volume and gas permeability but increases H 2 /CO 2 selectivity, which can be correlated with the molar ratio of the protons to PBI repeating units in the assemblies. Increasing the temperature decreases the H 2 /CO 2 selectivity because of weakened interactions. When challenged with model gas mixtures, a supramolecular assembly based on TMA shows H 2 /CO 2 separation properties superior to state-of-the-art materials and above Robeson's upper bound. Furthermore, this study elucidates the fruitful harnessing of dynamic non-covalent bonds to design robust and highly selective membranes for industrial gas separations.

36 MATERIALS SCIENCE↗
NASA NTRS1985

Free-surface phenomena under low- and zero-gravity conditions

A free surface experiment using a liquid doped with a fluorescent dye under sheet illumination is summarized. The work includes the selection of a CCD camera for use during the design stages of the experiment as well as a preliminary demonstration of this technique in the production of a contour map of a liquid-liquid interface with better than 0.1 mm resolution. With a different data sampling and storage procedure, the image processing is reduced to a simple thresholding procedure which can be done in hardware.

Hesselink, L.↗
DOE OSTI2025

A dual promotional effect of doping tantalum (Ta) in atomically dispersed Ru/CeO 2 catalyst toward CO 2 methanation: Enhanced associative adsorption of CO 2 and activation of H 2

Precisely controlling the product selectivity in CO 2 hydrogenation through rational catalyst design presents a promising approach to mitigate environmental and energy-related challenges, though it remains a significant scientific hurdle. Herein, the CH 4 selectivity of 0.5 wt% Ru loaded catalysts at 250 °C was effectively shifted from approximately 35 % to 100 % through the incorporation of Ta dopant into the CeO 2 support. The EXAFS spectra in conjunction with CO DRIFTS experiment indicated the presence of atomically dispersed Ru particles anchored on the Ta-doped CeO 2 surface. A higher oxidized CeO 2 surface was evidenced in the presence of Ta dopant. The presence of Ta dopant also improved the dispersion of Ru species and their interaction with the support. Most importantly, the Ru/Ta-CeO 2 catalyst exhibited a pronounced capacity for associative CO 2 -adsorption under atmospheric pressure at 50 °C. An improved H 2 activation was also observed under CO 2 hydrogenation conditions. This novel finding of the dual promotional effect of Ta carries a significant impact in the field of CO 2 capture and utilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

A mechanistic understanding of the roles of water is essential for developing highly active and selective catalysts for hydrodeoxygenation (HDO) reactions since water is ubiquitous in such reaction systems. Here, we present a study for phenol HDO on Fe catalysts using density functional theory which examines the effect of water on three elementary pathways for phenol HDO using an explicit solvation model. The presence of water is found to significantly decrease activation barriers required by hydrogenation reactions via two pathways. First, the proton transfer in the hydrogen bonding network of the liquid water phase is nearly barrierless, which significantly promotes the direct through space tautomerization of phenol. Second, due to the high degree of oxophilicity on Fe, liquid water molecules are found to be easily dissociated into surface hydroxyl groups that can act as Brønsted acid sites. These sites dramatically promote hydrogenation reactions on the Fe surface. As a result, the hydrogen assisted dehydroxylation becomes the dominant phenol HDO pathway. This work provides new fundamental insights into aqueous phase HDO of biomass-derived oxygenates over Fe-based catalysts; e.g., the activity of Fe-based catalysts can be optimized by tuning the surface coverage of Brønsted acid sites via surface doping.

Bronsted acid sites↗
DOE OSTI2014

Structural and thermodynamic consideration of metal oxide doped GeO{sub 2} for gate stack formation on germanium

A systematic investigation was carried out on the material and electrical properties of metal oxide doped germanium dioxide (M-GeO{sub 2}) on Ge. We propose two criteria on the selection of desirable M-GeO{sub 2} for gate stack formation on Ge. First, metal oxides with larger cation radii show stronger ability in modifying GeO{sub 2} network, benefiting the thermal stability and water resistance in M-GeO{sub 2}/Ge stacks. Second, metal oxides with a positive Gibbs free energy for germanidation are required for good interface properties of M-GeO{sub 2}/Ge stacks in terms of preventing the Ge-M metallic bond formation. Aggressive equivalent oxide thickness scaling to 0.5 nm is also demonstrated based on these understandings.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Carbon Defect Characterization of Nitrogen-Doped Reduced Graphene Oxide Electrocatalysts for the Two-Electron Oxygen Reduction Reaction

Numerous modified-carbon catalysts have been developed for the direct synthesis of hydrogen peroxide through electrochemical oxygen reduction. Yet, given the complex structure of most porous carbons and the poor oxygen reduction reaction (ORR) selectivity typically observed when they are used as catalysts, it is still unclear which carbon defects are responsible for the high two-electron ORR activity typically observed in these materials. Here, we study electrocatalytic peroxide formation activity of nitrogen-doped reduced graphene oxide ( N -rGO) materials to relate carbon defects to electrocatalytic activity. To achieve this, we selected two N -rGO electrodes that selectively produce peroxide at all potentials studied (0.70–0.10 V vs RHE) under alkaline conditions. Oxygen reduction studies, combined with material characterization, especially solid-state 13 carbon nuclear magnetic resonance coupled with magic angle spinning and cross-polarization, demonstrate that epoxy or ether groups in the N -rGO catalyst are likely associated with the active sites that form peroxide at the lowest overpotential in alkaline media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Designing Boron Nitride Islands in Carbon Materials for Efficient Electrochemical Synthesis of Hydrogen Peroxide

Heteroatom-doped carbons have drawn increasing research interest as catalysts for various electrochemical reactions due to their unique electronic and surface structures. In particular, co-doping of carbon with boron and nitrogen has been shown to provide significant catalytic activity for oxygen reduction reaction (ORR). However, limited experimental work has been done to systematically study these materials, and much remains to be understood about the nature of the active site(s), particularly with regards to the factors underlying the activity enhancements of these boron–carbon–nitrogen (BCN) materials. Herein, we prepare several BCN materials experimentally with a facile and controlled synthesis method, and systematically study their electrochemical performance. We demonstrate the existence of h -BN domains embedded in the graphitic structures of these materials using X-ray spectroscopy. These synthesized structures yield higher activity and selectivity toward the 2e – ORR to H 2 O 2 than structures with individual B or N doping. We further employ density functional theory calculations to understand the role of a variety of h -BN domains within the carbon lattice for the ORR and find that the interface between h -BN domains and graphene exhibits unique catalytic behavior that can preferentially drive the production of H 2 O 2 . Here, to the best of our knowledge, this is the first example of h -BN domains in carbon identified as a novel system for the electrochemical production of H 2 O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Low resistance Ohmic contact to p-type crystalline silicon via nitrogen-doped copper oxide films

This work explores the application of transparent nitrogen doped copper oxide (CuO{sub x}:N) films deposited by reactive sputtering to create hole-selective contacts for p-type crystalline silicon (c-Si) solar cells. It is found that CuO{sub x}:N sputtered directly onto crystalline silicon is able to form an Ohmic contact. X-ray photoelectron spectroscopy and Raman spectroscopy measurements are used to characterise the structural and physical properties of the CuO{sub x}:N films. Both the oxygen flow rate and the substrate temperature during deposition have a significant impact on the film composition, as well as on the resulting contact resistivity. After optimization, a low contact resistivity of ∼10 mΩ cm{sup 2} has been established. This result offers significant advantages over conventional contact structures in terms of carrier transport and device fabrication.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Selective and Stable Ethanol Synthesis via Electrochemical CO 2 Reduction in a Solid Electrolyte Reactor

Electrochemical CO 2 reduction to ethanol faces challenges such as low selectivity, a product mixture with liquid electrolyte, and poor catalyst/reactor stability. Here, we developed a grain-rich zinc-doped Cu 2 O precatalyst that presented a high ethanol Faradaic efficiency of over 40% under a current density of 350 mA·cm –2 . Our density functional theory (DFT) simulation suggested that Zn atoms inside the structure have a greater carbophilicity than the Cu atoms to help facilitate *CHCHO formation, a key reaction intermediate toward ethanol instead of other C 2 products. Here, a high Faradaic efficiency ratio between ethanol and ethylene (FE EtOH /FE C2H4 ) reached 2.34 in the zinc-doped Cu 2 O precatalyst, representing an over 4-fold improvement compared to bare Cu 2 O precatalyst. By integrating this Cu-based catalyst into a porous solid electrolyte (PSE) reactor with a salt-managing design, we achieved stable ethanol production for over 180 h under a current density of 250 mA·cm –2 while maintaining ethanol selectivity at ~30%.

09 BIOMASS FUELS↗
DOE OSTI2017

Structural and Dielectric Properties of Rare Earth Doped Lithium Nanoferrites for Sensing Applications

Nowadays it is the hot topic to analyze the behavior of different materials towards gasses so that they can be used for sensing purpose. Ferrites specifically lithium ferrites show very good response to gasses present in the environment. Lithium ferrite doped with Gd (Li{sub 0.5}Fe{sub 2.475}Gd{sub 0.025}O{sub 4}) was selected for this purpose. Sample was synthesized by simplified sol-gel technique. After that, pellets were formed and sintered at different temperatures. Spinel cubic phase was observed in x-ray diffraction (XRD). It is noted that by increasing sintering temperature, results slightly decrease in lattice constant. Scanning electron microscopy (SEM) was used to study the surface morphology of the samples. It was observed that particles were spherical in shape. AC electrical properties were studied at room temperature in the frequency range of 20 Hz to 3 MHz. AC electrical conductivity and dielectric constant decreased with the increase in sintering temperature. The maximum conductivity was observed in the sample that was sintered at temperature of 700 {sup ∘}C. Significant variation in electrical response with frequency made these samples suitable for sensing applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

High-Selectivity Electrochemical Conversion of CO 2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode

Carbon dioxide is a pollutant, but also a potential carbon source provided an efficient means to convert it to useful products. Herein we report a nanostructured catalyst for the direct electrochemical reduction of dissolved CO 2 to ethanol with high Faradaic efficiency (63%) and high selectivity (84%). The catalyst is comprised of Cu nanoparticle on a highly textured, N-doped graphene film. Detailed electrochemical analysis and complementary DFT calculations indicate a novel mechanism in which multiple active sites, working sequentially, control the coupling of carbon monoxide radicals and mediate the subsequent electrochemical reduction to alcohol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Nitrogen-Doped Graphene Oxide Electrocatalysts for the Oxygen Reduction Reaction

Platinum group metal-free (PGM-free) electrocatalysts for the oxygen reduction reaction (ORR) often exhibit a complex functionalized graphitic structure. Because of this complex structure, limited understanding exists about the design factors for the synthesis of high-performing materials. Graphene, a two-dimensional hexagonal structure of carbon, is amenable to structural and functional group modifications, making it an ideal analogue to study crucial properties of more complex graphitic materials utilized as electrocatalysts. In this paper, we report the synthesis of active nitrogen-doped graphene oxide catalysts for the ORR in which their activity and four-electron selectivity are enhanced using simple solvent and electrochemical treatments. The solvents, chosen based on Hansen’s solubility parameters, drive a substantial change in the morphology of the functionalized graphene materials by (i) forming microporous holes in the graphitic sheets that lead to edge defects and (ii) inducing 3D structure in the graphitic sheets that promotes ORR. Additionally, the cycling of these catalysts has highlighted the multiplicity of the active sites, with different durability, leading to a highly selective catalyst over time, with a minimal loss in performance. High ORR activity was demonstrated in an alkaline electrolyte with an onset potential of ~1.1 V and half-wave potential of 0.84 V vs RHE. Furthermore, long-term stability potential cycling showed minimal loss in half-wave potential (<3%) in both N 2 - and O 2 -saturated solutions with improved selectivity toward the four-electron reduction after 10000 cycles. Lastly, the results described in this work provide additional understanding about graphitic electrocatalysts in alkaline media that may be utilized to further enhance the performance of PGM-free ORR electrocatalysts.

36 MATERIALS SCIENCE↗