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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Visualization of facet-dependent pseudo-photocatalytic behavior of TiO 2 nanorods for water splitting using In situ liquid cell TEM

Here, we report an investigation of the pseudo-photocatalytic behavior of rutile TiO 2 nanorods for water splitting observed with liquid cell transmission electron microscopy (TEM). The electron beam serves as a “light” source to initiate the catalytic reaction and a “water-in-salt” aqueous solution is employed as the electrolyte. The observation reveals that bubbles are generated preferentially residing near the {110} facet of a rutile TiO 2 nanorod under a low electron dose rate (9.3–18.6 e-/Å 2 ·s). These bubbles are ascribed to hydrogen gas generated from the pseudo-photocatalytic water splitting. As the electron beam current density increases to 93 e-/Å 2 ·s, bubbles are also found at the {001} and {111} facets as well as in the bulk liquid solution, demonstrating the dominant effects of water electrolysis by electron beam under higher dose rates. The facet-dependent pseudo-photocatalytic behavior of rutile TiO 2 nanorods is further validated using density functional theory (DFT)calculation. Finally, our work establishes a facile liquid cell TEM setup for the study of pseudo-photocatalytic water splitting and it may also be applied to investigation of other photo-activated phenomena occurring at the solid-liquid interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Facet-selective nucleation and conformal epitaxy of Ge shells on Si nanowires

Knowledge of nanoscale heteroepitaxy is continually evolving as advances in material synthesis reveal new mechanisms that have not been theoretically predicted and are different than what is known about planar structures. In addition to a wide range of potential applications, core/shell nanowire structures offer a useful template to investigate heteroepitaxy at the atomistic scale. We show that the growth of a Ge shell on a Si core can be tuned from the theoretically predicted island growth mode to a conformal, crystalline, and smooth shell by careful adjustment of growth parameters in a narrow growth window that has not been explored before. In the latter growth mode, Ge adatoms preferentially nucleate islands on the {113} facets of the Si core, which outgrow over the {220} facets. Islands on the low-energy {111} facets appear to have a nucleation delay compared to the {113} islands; however, they eventually coalesce to form a crystalline conformal shell. As a result, synthesis of epitaxial and conformal Si/Ge/Si core/multishell structures enables us to fabricate unique cylindrical ring nanowire field-effect transistors, which we demonstrate to have steeper on/off characteristics than conventional core/shell nanowire transistors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Facet-Dependent Kinetics and Energetics of Hematite for Solar Water Oxidation Reactions

Currently, the performance of a photoelectrochemical (PEC) system is highly dependent on the charge separation, transport and transfer characteristics at the photoelectrode|electrolyte interface. Of the factors that influence the charge behaviors, the crystalline facets of the semiconductor in contact with the electrolyte play an important role but has been poorly studied previously. Here, we present a study aimed at understanding how the different facets of hematite affect the charge separation and transfer behaviors in a solar water oxidation reaction. Specifically, hematite crystallites with predominantly {012} and {001} facets exposed were synthesized. Density functional theory (DFT) calculations revealed that hematite {012} surfaces feature higher OH coverage, which was confirmed by X-ray photoelectron spectroscopy (XPS). These surface OH groups act as active sites to mediate water oxidation reactions, which plays a positive role for the PEC system. These surface OH groups also facilitate charge recombination, which compromises the charge separation capabilities of hematite. Moreover, intensity modulated photocurrent spectroscopy (IMPS) confirmed that hematite {012} surfaces exhibit higher rate constants for both charge transfer and recombination. Open circuit potential (OCP) measurements revealed that the hematite {012} surface reflects a greater degree of Fermi level pinning effect. Our results shed light on how different surface crystal structures may change surface kinetics and energetics. The information is anticipated to contribute to efforts on optimizing PEC performance for practical solar fuel synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Machine-Learning Methods Enable Exhaustive Searches for Active Bimetallic Facets and Reveal Active Site Motifs for CO 2 Reduction

Bimetallic catalysts are promising for the most difficult thermal and electrochemical reactions, but modeling the many diverse active sites on polycrystalline samples is an open challenge. Here, we present a general framework for addressing this complexity in a systematic and predictive fashion. Active sites for every stable low-index facet of a bimetallic crystal are enumerated and cataloged, yielding hundreds of possible active sites. The activity of these sites is explored in parallel using a neural-network-based surrogate model to share information between the many density functional theory (DFT) relaxations, resulting in activity estimates with an order of magnitude fewer explicit DFT calculations. Sites with interesting activity were found and provide targets for follow-up calculations. This process was applied to the electrochemical reduction of CO 2 on nickel gallium bimetallics and indicated that most facets had similar activity to Ni surfaces, but a few exposed Ni sites with a very favorable on-top CO configuration. This motif emerged naturally from the predictive modeling and represents a class of intermetallic CO 2 reduction catalysts. These sites rationalize recent experimental reports of nickel gallium activity and why previous materials screens missed this exciting material. Most importantly these methods suggest that bimetallic catalysts will be discovered by studying facet reactivity and diversity of active sites more systematically.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Facet effects on generation-recombination currents in semiconductor laser diodes

The contribution of facet defect currents to the overall generation-recombination current of laser diodes operating near 800 nm is quantified experimentally, using the dependence of current on cavity length to isolate facet effects. Here the results show that facet currents exhibit an ideality factor much greater than 2, while currents associated with the interior of the laser diode stripes exhibit an ideality factor of 2. These differences in behavior provide an approach to infer additional details of defect evolution in aging studies of semiconductor laser diodes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

24% Single-Junction GaAs Solar Cell Grown Directly on Growth-Planarized Facets Using Hydride Vapor Phase Epitaxy

A 24%-efficient single-junction GaAs solar cell grown directly on a faceted, spalled (100) GaAs substrate after in situ planarization growth by hydride vapor phase epitaxy (HVPE) is achieved. Controlled spalling, a promising low-cost substrate reuse technique, produces large facets in (100)-oriented GaAs substrates due to the orientation of the fracture planes used for lift-off. Planarization by HVPE offers a path toward direct use of these spalled substrates without costly polishing steps. In this report the growth rate anisotropy enabling planarization arising from diffusion and differences in the adsorption of growth species on {n11}B-type facets relative to (100) is determined. Consecutive planarization and device growth that results in a solar cell with a minimal performance difference relative to a control cell grown on an epitaxy-ready substrate are demonstrated. These results show that controlled spalling coupled with HVPE planarization is a viable pathway for lowering the cost of III-V photovoltaics.

14 SOLAR ENERGY↗
DOE OSTI2025

Electrosynthesis of high purity ethylene using high-index facet Cu 2 O nanocrystals electrocatalyst

Electrochemical CO 2 reduction reaction (eCO2RR) to multi-carbon (C 2+ ) products with copper-based catalysts is often limited by poor selectivity. This challenge arises from the concurrent formation of various intermediates, dictated by the atomic arrangement and electronic properties of surface atoms. In this study, we found that copper (I) oxide (Cu 2 O) nanocrystals with 50 facets (50F-NC), predominantly featuring (211) facets that offers high density of under-coordinated sites, demonstrate superior ethylene (C 2 H 4 ) selectivity of 92% ± 2 with an overall current density of 212 mA/cm 2 at -650 mV vs RHE. Furthermore, after one month of storage in a 1 M KOH electrolyte, this catalyst demonstrated a C 2 H 4 Faradaic efficiency of 87% highlighting its stabile structure under strong alkaline environments. Here, operando electrochemical Raman spectroscopy revealed enhanced CO* intermediate coverage on the 50F-NC catalyst, correlating with improved C-C coupling. SEM, TEM, and XPS analyses, along with DFT calculations, suggested that Cu sites on the (211) facet of 50F-NC and those at the Cu/Cu 2 O interface formed in-situ due to the surface reconstruction during the reaction, are likely active sites for effective C-C coupling and sustained high-rate C 2 H 4 production.

Cu nano particle↗
DOE OSTI2014

Facile synthesis of gold nanopuncheons with high-index facets and their SERS effects on Rhodamine 6G

Highlights: • Au nanopuncheons with high-index facets have been prepared by seed-mediated growth. • The nanopuncheons are enclosed by 24 planes of (2 5 0), (3 0 1) and 2 (0 1 0) planes. • The nanopuncheons showed high SERS activity toward Rhodamine 6G. - Abstract: Au nanopuncheons with exposed high-index facets have been synthesized in high-yield by employing didodecyldimethylammonium bromide (DDAB) as surfactant in one-step seed-mediated growth. Transmission electron microscopy (TEM) characterization showed that the as-prepared Au nanopuncheons possessed 24 high index facets of (2 5 0), (3 0 1), and 2 (0 1 0) planes. Due to the high density of atomic steps and kinks in the structure, the Au nanopuncheons exhibited high surface enhanced Raman scattering (SERS) activity toward Rhodamine 6G.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Facet-Dependent Photodegradation of Methylene Blue by Hematite Nanoplates in Visible Light

The expression of specific crystal facets in different nanostructures is known to play a vital role in determining the sensitivity toward photodegradation of organics, which can generally be ascribed to differences in surface structure and energy. Herein, we report the synthesis of hematite nanoplates with controlled relative exposure of basal (001) and edge (012) facets, enabling us to establish direct correlation between surface structure and the photocatalytic degradation efficiency of methylene blue (MB) in the presence of hydrogen peroxide. MB adsorption experiments showed that the capacity on (001) is about three times larger than on (012), and this is supported by density functional theory calculations suggesting adsorption energies about 1.5 times higher. However, this alone cannot explain the observed MB photodegradation rate, which is around 14.5 times faster on (001) than (012). The enhancement we attribute to a higher availability of photoelectron accepting surface Fe3+ sites on the (001) facet. This facilitates more efficient iron valence cycling and the heterogeneous photo-Fenton reaction yielding MB-oxidizing hydroxyl radicals at the surface. Our findings help establish a rational basis for design and optimization of hematite nanostructures as photocatalysts for environmental remediation.

Zong, Meirong↗
DOE OSTI2019

Facet-Specific Photocatalytic Degradation of Organics by Heterogeneous Fenton Chemistry on Hematite Nanoparticles

Hematite nanoparticles are abundant in the photic zone of aquatic environments, where they play a prominent role in photocatalytic transformations of bound organics. In this work, we examine the photocatalytic degradation of rhodamine B (RhB) by visible light using two different structurally well-defined hematite nanoparticle morphologies. In addition to detailed solids characterization and aqueous kinetics measurements, we also exploit species-selective scavengers in electron paramagnetic spectroscopy (EPR) to sequester specific reaction channels and thereby assess their impact. Photodegradation rates for nanoplates dominated by {001} facets and nanocubes dominated by {012} facets were 0.13 and 0.7 h -1 , respectively, and turn over frequencies for the active sites on {001} and {012} were 7.89 × 10 -3 and 3.07× 10 -3 s -1 , yielding apparent activation energies of 17.13 and 24.94 kcal/mol within the energetic span model. Facet-specific differences appear directly linked not with the simple aerial cation site density but instead with their extent of undercoordination. By establishing this linkage, the findings lay a foundation for predicting the photocatalytic degradation efficiency for the myriad of possible hematite nanoparticle morphologies, and more broadly help unveil key reactions at the interface that may govern photocatalytic organic transformations in natural and engineered aquatic environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Facet Impact of CuMn 2 O 4 Spinel Nanocatalysts on Enhancement of the Oxygen Reduction Reaction in Alkaline Media

Surface-structure engineering represents an attractive strategy to optimize the energy conversion performance of nanocatalysts using their deliberately controlled exposed facets. To further exploit the potential of non-PGM-based spinel catalysts for alkaline oxygen reduction reaction (ORR), a cathodic fuel cell reaction, we hereby report a strategy of ORR improvement by controlling the crystallographic facets of ultra-small CuMn 2 O 4 spinel nanocatalysts through a developed colloidal synthesis approach. The synthesis of CuMn 2 O 4 nanocrystals with morphological control relies on the design and selection of the Cu-/Mn-precursors with striking discrepancies in reaction kinetics. Following carbon loading and an annealing post-treatment of the as-synthesized nanocatalysts, the exclusively {101} facet-exposed CuMn 2 O 4 spinel nano-octahedra exhibit improved electrocatalytic activity toward ORR in 1 M KOH, when compared to their spherical counterparts, exhibiting a mass activity (MA) of 37.6 A/g at 0.85 V. After 10,000 cycles of ORR durability test, the nano-octahedra still retain an MA of 24.5 A/g, which is twice that of the CuMn 2 O 4 spinel nanospheres. Structural characterizations after durability testing indicate that the MA decay is likely associated with a decrease in the Mn 3+ fraction and the emergence of Cu + on CuMn 2 O 4 nano-octahedral surfaces. Finally, as a paradigm, this synthesis approach could be extended to other Mn-based spinel nanocatalysts with precise shape control, enabling us to understand and establish the relationship between the surface lattice/valence state and electrocatalytic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Single-Facet Dominant Anatase TiO 2 (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration

Alkanol dehydration on Lewis acid-base pairs of transition metal oxide catalysts is a reaction of importance in oxygen removal from biomass-derived feedstocks and their conversion to chemicals in general. However, catalysts with a high degree of structural heterogeneity, such as commercial TiO 2 powders, are not well-suited to establish rigorous structure-function relationships at an atomic level. Here, we provide compelling evidence for the effects of surface orientation of TiO 2 catalyst on elimination reactions of alcohols. Two anatase titania model catalysts, with preferential exposure of (101) and (001) facets, were synthesized and studied for 2-propanol dehydration using kinetic, isotopic, microscopic, and spectroscopic measurements, coupled with DFT calculations. Surface Lewis acid sites were found to be active for 2-propanol dehydration and (101) facets are more reactive than (001) facets under the reaction conditions studied. On both anatase surfaces, 2-propanol was found to dehydrate via concerted E2 elimination pathways, but with different initial states and thus also different intrinsic activation barriers. Molecular 2-propanol dehydration dominates on TiO2 (101) while on TiO 2 (001), 2-propanol simultaneously converts to more stable 2-propoxide before dehydration, which then requires higher activation energies for E2 elimination.

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

Glycerol Electrooxidation over Precision-Synthesized Gold Nanocrystals with Different Surface Facets

Electrochemical glycerol oxidation (EGO) emerges as a promising route to valorize glycerol, an underutilized byproduct from biodiesel production, into value-added chemicals. This study employed three types of gold (Au) nanocrystals with controlled shapes to elucidate the facet-dependent electrocatalytic behavior in EGO. Octahedral, rhombic dodecahedral, and cubic Au nanocrystals with {111}, {110}, and {100} facets, respectively, were precisely synthesized with uniform size and shape. Rhombic dodecahedra exhibited the lowest onset potential for EGO due to facile AuOH formation, while octahedra showed enhanced electrochemical activity for glycerol oxidation and resistance to poisoning. In-situ FTIR analysis revealed that Au {111} surfaces selectively favored C 2 products, whereas Au {100} surfaces promoted C 3 product formation, highlighting the significant effect of facet orientation on EGO performance and informing catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Stable platinum nanoparticles on specific MgAl 2 O 4 spinel facets at high temperatures in oxidizing atmospheres

The development of thermally stable, nanometer-sized precious metal-based catalysts remains a daunting challenge. Such materials, especially those based on the use of costly platinum metal, are essential and, to date, non-replaceable for a large number of industrially important catalytic processes. Here we report a well-defined cuboctahedral MgAl 2 O 4 spinel support material that is capable of stabilizing platinum particles in the range of 1–3 nm on its relatively abundant {111} facets during extremely severe aging at 800 °C in air for 1 week. The aged catalysts retain platinum dispersions of 15.9% with catalytic activities for methanol oxidation being ~80% of that of fresh ones, whereas a conventional Pt/γ-Al 2 O 3 catalyst is severely sintered and nearly inactive. Finally, we reveal the origin of the markedly superior ability of spinel {111} facets, resulting from strong interactions between spinel surface oxygens and epitaxial platinum {111} facets, inspiring the rational design of anti-sintering supported platinum group catalysts.

anti-sintering↗
DOE OSTI2021

Facet-selective morphology-controlled remote epitaxy of ZnO microcrystals via wet chemical synthesis

We report on morphology-controlled remote epitaxy via hydrothermal growth of ZnO micro- and nanostructure crystals on graphene-coated GaN substrate. The morphology control is achieved to grow diverse morphologies of ZnO from nanowire to microdisk by changing additives of wet chemical solution at a fixed nutrient concentration. Although the growth of ZnO is carried out on poly-domain graphene-coated GaN substrate, the direction of hexagonal sidewall facet of ZnO is homogeneous over the whole ZnO-grown area on graphene/GaN because of strong remote epitaxial relation between ZnO and GaN across graphene. Atomic-resolution transmission electron microscopy corroborates the remote epitaxial relation. The non-covalent interface is applied to mechanically lift off the overlayer of ZnO crystals via a thermal release tape. The mechanism of facet-selective morphology control of ZnO is discussed in terms of electrostatic interaction between nutrient solution and facet surface passivated with functional groups derived from the chemical additives.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Highly ordered self-assembled nanoscale periodic faceting in GaAs(631) homoepitaxial growth

We report on the self-assembly of large-order-correlated nanoscale faceting on GaAs(631)A substrates grown by molecular beam epitaxy. The surface morphology of the grown samples as a function of the growth temperature and the As-beam equivalent pressure was studied using atomic force microscopy. A two-dimensional autocorrelation function analysis was performed in order to quantitatively determine the uniformity of the surface corrugation. By optimizing the growth conditions, correlated faceted areas as large as 1.7 Multiplication-Sign 1.7 {mu}m{sup 2} are obtained. The highly ordered surface corrugation discussed here provides useful insights to prepare highly ordered facet planes for the self organized growth of quantum wires.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Transverse effects in plasma wakefield acceleration at FACET - Simulation studies

We investigate transverse effects in the plasma-wakefield acceleration experiments planned and ongoing at FACET. We use PIC simulation tools, mainly QuickPIC, to simulate the interaction of the drive electron beam and the plasma. In FACET a number of beam dynamics knobs, including dispersion and bunch length knobs, can be used to vary the beam transverse characteristics in the plasma. We present simulation results and the status of the FACET experimental searches.

43 PARTICLE ACCELERATORS↗
DOE OSTI2014

High-power, low-lateral divergence broad area quantum cascade lasers with a tilted front facet

We introduce a simple technique to improve the beam quality of broad area quantum cascade lasers. Moderately tilted front facets of the laser provide suppression of higher order lateral waveguide modes. A device with a width of 60 μm and a front facet angle of 17° shows a nearly diffraction limited beam profile. In addition, the peak output power and the slope efficiency of the device are increased since most of the light inside the cavity is emitted through the tilted front facet by an asymmetric light intensity distribution along the cavity.

43 PARTICLE ACCELERATORS↗